JPH0556394B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an adhesive for bonding a dental polysulfone resin and a dental acrylic resin.

BACKGROUND OF THE INVENTION Conventional dental prostheses made of resin have been produced using acrylic resins for many years by a pressure molding method using heat polymerization of polymers and monomers. This had the advantage that repairs were easy because the same acrylic polymer powder and acrylic monomer liquid were used as repair materials.

However, dental prostheses obtained by heating polymerization of such acrylic resins are brittle, and their thin parts often break due to occlusal force, which is a strength disadvantage, as well as the heating polymerization reaction is often insufficient. ,
It also had hygienic drawbacks, such as residual monomers leaching out and causing allergic symptoms.

Additionally, artificial teeth made of acrylic resin have the disadvantage that they are easily abraded by toothbrushes.

Dental prostheses made of polysulfone resin have been proposed and have come into practical use as a solution to the drawbacks of dental prostheses made of acrylic resin.

This polysulfone resin is a type of engineering plastic with high mechanical strength and excellent impact resistance, but it has poor adhesion with the commonly used acrylic resin artificial teeth and requires special maintenance devices. Even when ordinary adhesives are used, the adhesion is still insufficient, and there are practical problems such as the fact that the artificial teeth tend to come off when biting into relatively hard food, for example.

In addition, so-called rebase agents such as acrylic resin hard lining agents and temporary lining agents, which are used to adjust the wall thickness of the mouth part of acrylic resin denture bases, are applied to the polysulfone resin dental prosthesis. However, the actual situation was that sufficient adhesion could not be obtained and it could not be put to practical use.

Problems to be Solved by the Invention An object of the present invention is to provide a dental adhesive that can firmly bond a dental polysulfone resin and a dental acrylic resin. In other words, we strongly bonded polysulfone resin denture bases and acrylic resin artificial teeth, polysulfone resin denture bases and acrylic resin rebase agents, acrylic resin denture bases and polysulfone resin artificial teeth, etc., and their practicality. This provides an adhesive that dramatically expands the range of adhesives.

Means for Solving the Problems The present invention is characterized in that the adhesive used to bond dental polysulfone resin and dental acrylic resin is a chlorinated solvent having a boiling point of 30 to 150°C. It consists of aromatic polyester copolymer or polyester carbonate, and the amount of aromatic polyester copolymer or polyester carbonate is 0.3 to 20 parts by weight per 100 parts by weight of the solvent.
This is a dental adhesive containing part by weight.

The aromatic polyester copolymer used in the present invention is a mixture of terephthalic acid and isophthalic acid or functional derivatives thereof (the molar ratio of terephthalic acid groups to isophthalic acid groups is 9:1 to 1:9). and 2,2-bis(4'-hydroxyphenyl)propane (hereinafter abbreviated as bisphenol A).

A method for producing such an aromatic polyester copolymer is so-called interfacial polymerization (WMEareckson. J.Poly.
Sci.
Ind.Eng.Chem. 51 147, 1959, Special Publication 37-
5599), melt polymerization of aromatic dicarboxylic acids and bisphenols by heating in the presence of acetic anhydride (Tokuko Sho
38-15247), and melt polymerization in which aromatic dicarboxylic acids and bisphenols are heated in the presence of diaryl carbonate (Japanese Patent Publication No. 38-26299).

The polyester carbonate used in the present invention is obtained from (A) aromatic dicarboxylic acid and/or its functional derivative, (B) aromatic dihydroxy compound and/or its functional derivative, (C) diaryl carbonate or phosgene. be. Specific examples of component (A) include terephthalic acid, isophthalic acid, methyl terephthalic acid, methyl isophthalic acid, diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, naphthalene dicarboxylic acid, or ester-forming derivatives thereof, such as lower alkyl Examples include esters, phenyl esters, and acid halides. Specific examples of component (B) include hydroquinone, resorcinol, 2,2-bis(4
-hydroxyphenyl)propane (bisphenol A), 4,4'-dihydroxydiphenyl, 1,
1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)
Ethane, bis(4-(4-hydroxyphenyl)
Methane, 2,2-bis(4-hydroxy-3,5
-dibromophenyl)propane, 4,4'-dihydroxydiphenylsulfone, 1,2-bis(4-
Examples include hydroxyphenyl)ethane and ester-forming derivatives thereof. One or more of these may be used. Among these, bisphenol A is particularly preferred. Examples of the diaryl carbonate of component (C) include diphenyl carbonate, dicresyl carbonate, di-β-naphthyl carbonate, and bis(2-chlorophenyl) carbonate. Among these combinations, terephthalic acid (or terephthalic acid diphenyl ester), bisphenol A and diphenyl carbonate are particularly preferably used.

The polyester carbonate used as a component of the composition of the present invention can be produced from the three components (A), (B), and (C) by any method such as bulk polycondensation, solution polycondensation, and interfacial polycondensation.

The chlorinated solvents with a boiling point of 30 to 150°C used in the present invention include methylene chloride (boiling point 40°C),
Ethylene chloride (boiling point 84℃), chloroform (boiling point
62℃), trichlorethylene (boiling point 87℃), 1,
1,1-trichloroethane (boiling point 74℃), 1,1,
These include 2-trichloroethane (boiling point 114°C), tetrachlorethylene (boiling point 121°C), and tetrachloroethane (boiling point 129°C).

If the boiling point is too high, it will not be easy to remove the solvent after application to polysulfone resin or acrylic resin, and if the boiling point is too low, the solution concentration will change significantly.
Moreover, since the coating workability is not good, it is appropriate to use a material having a boiling point of 30 to 150°C.

In particular, methylene chloride has a low boiling point and dries quickly, so it does not cause any cracks when applied to dental polysulfone resins. In addition, it is a good solvent for aromatic polyester copolymers and polyester carbonates, and it is easy to prepare a uniform solution, and it also has good affinity with dental acrylic resins. Furthermore, it is favorable in terms of safety and hygiene, and is therefore preferable.

Furthermore, in the present invention, the content of the aromatic polyester copolymer or polyester carbonate in the chlorinated solvent is 100 parts by weight of the aromatic polyester copolymer or polyester carbonate (hereinafter abbreviated as the resin). A suitable amount is 0.3 to 20 parts by weight.

If the resin is less than 0.3 parts by weight with respect to 100 parts by weight of the solvent, the adhesion between the dental polysulfone resin and the dental acrylic resin will not be sufficient, and if the resin content exceeds 20 parts by weight, The viscosity of the solution is too high, making uniform application difficult and undesirable. Furthermore, when the content of the resin is 0.5 to 15 parts by weight, the adhesive has well-balanced properties in terms of workability, drying efficiency, adhesive strength, etc., which is preferable.

Polymethyl methacrylate (hereinafter abbreviated as PMMA) and methyl methacrylate monomer (hereinafter abbreviated as MMA) can be blended into the resin solution used in the present invention in an appropriate amount depending on the purpose.

For example, when using the resin solution to bond a polysulfone denture base and an acrylic resin revealer, adding an appropriate amount of PMMA to the solution will achieve stronger adhesion; It has the effect of giving gloss to the part and its periphery, giving it a better appearance.

In addition, one or more conventional additives such as colorants such as dyes and pigments, ultraviolet absorbers, and stabilizers may be added to the resin solution used in the present invention, within a range that does not impair the purpose of the present invention. can do.

Furthermore, the dental polysulfone resin as used in the present invention refers to polyarylene polyether polysulfone in which arylene units are located in a disordered or ordered manner together with ether and sulfone bonds, such as UCC polysulfone Udel with the structure Polyethersulfone manufactured by ICI with the structure of
Refers to highly hygienic resins and compounds that can be used as dental prostheses, including Victrex.

The dental acrylic resin referred to in the present invention is MMA
Refers to acrylic resins used as dental prosthetics, such as homopolymers of (PMMA) and copolymers with other methacrylates such as butyl methacrylate.

The method of bonding dental polysulfone resin and dental acrylic resin with the adhesive of the present invention is not particularly limited. For example, the adhesive of the present invention is applied to one or both adherend surfaces, air-dried for several seconds to several minutes, then both adherend surfaces are brought together, lightly pressed, and then further heated at 80°C to 150°C for 10 minutes. A method of performing heat treatment for about 100 minutes, a method of molding melted and softened polysulfone resin for denture base formation on an acrylic resin artificial tooth coated with the adhesive of the present invention under contact pressure, and cooling and solidifying it. Any method can be applied, such as applying the adhesive of the present invention on a polysulfone resin dental prosthesis, air-drying it, and then applying a commercially available acrylic resin rebase agent.

Function Surprisingly, when the aromatic polyester copolymer or polyester carbonate solution of the present invention is interposed at the adhering interface of polysulfone resin or acrylic resin and the solvent is removed by air drying or appropriate heat treatment, it becomes extremely strong. Adhesive strength can be obtained.

This is an aromatic polyester copolymer or polyester carbonate, polysulfone resin,
Although it has an essential molecular structure difference from acrylic resins, it has a relatively high affinity for both polysulfone resins and acrylic resins, and a good dispersion state close to the molecular level can be achieved at the adhesive interface. It is presumed that the

The present invention will be specifically explained below with reference to Examples, but these are merely exemplifications of preferred embodiments, and the present invention is not limited to the scope of the Examples.

Example 1 According to the artificial tooth fracture test method described in the Japanese Industrial Standard JIS T-6511, an acrylic resin artificial tooth (GC acrylic resin front tooth) 1 was prepared as shown in Figure 1.
was planted in the paraffin wax model so that the line connecting the incisal end 1' and the tooth neck 1'' was at a 45° angle with the paraffin wax model, and after burying the plaster in a flask, flowing wax was used to form a plaster model. Ta.

This plaster mold was installed in an injection molding machine at a cylinder temperature of 350℃, an injection pressure of 1500Kg/cm ² , and an injection speed.
200mm/sec (molding machine: Sumitomo-Nestal P40/25)
Under these conditions, a molten polysulfone resin (Udel P-1700 manufactured by UCC) colored like gums was injected into the flask.

After cooling, the flask was divided and molded articles for artificial tooth fracture testing were taken out. When the artificial tooth was squeezed strongly by hand, it came off from the molded product. Add 100 parts by weight of methylene chloride, an aromatic polyester copolymer (a methylene chloride solution of a mixed acid chloride with a ratio of terephthalic acid dichloride/isophthalic acid dichloride of 1:1, and an alkaline aqueous solution of bisphenol A) to the cavity where the artificial tooth has come off. obtained by interfacial polymerization method,
A solution consisting of 10 parts by weight of phenol/tetrachloroethane (with a logarithmic viscosity of 0.62 in a 6:4 weight ratio) was applied with a brush, and after air-drying for a few seconds, the acrylic resin artificial tooth that had been removed earlier was inserted. , lightly pressurized. Thereafter, heat treatment was performed for 40 minutes in a hot air drying oven at 80°C.

The resin bed part 2 of the obtained molded product was fixed with a holder 3 as shown in Fig. 1, and a fracture test was performed on the other artificial tooth end part 1 via a specified metal fitting 4 at a load creepage of 12 kgf/min. .

The fracture strength was 28 Kgf, a sufficiently high value that poses no problem in practical use.

Comparative Example 1 In the same manner as in Example 1, polysulfone resin was injected into the flask, and after cooling, the flask was divided, and the molded product for the artificial tooth fracture test was taken out. A similar fracture test was conducted.

The fracture strength was only 7 kgf, a low value that would pose a practical problem.

Example 2 A flask in which a denture base wax model in which acrylic resin artificial teeth (trade name: GC Acrylic Resin anterior teeth and molars) was implanted was heated,
The wax was softened and flowed to form a plaster mold. After that, polyether sulfone (made by ICI)
A U-shaped molded product (Victrex 4100G) colored to resemble the gums (U-shaped with a size corresponding to the alveolar ridge) is placed on the plaster mold in the lower flask,
The molded article was softened by blowing hot air at 350°C. When the mixture had sufficiently softened, the upper and lower flasks were combined and compression molded, followed by natural cooling.

After cooling, the upper and lower flasks were separated and the denture base was taken out.

When the patient squeezed the artificial tooth strongly by hand, the artificial tooth came off the denture base. Add 100 parts by weight of chloroform to the cavity of the artificial tooth, and add polyester carbonate (obtained by bulk polycondensation from terephthalic acid, bisphenol A, and diphenyl carbonate, as a basic structure) A solution consisting of 15 parts by weight of polyester carbonate with an ester/carbonate ratio (m/n) of 51/49 and an intrinsic viscosity of 0.655 measured at 25°C in chloroform was applied with a brush and air-dried for a few seconds. After that, the acrylic resin artificial tooth that had been removed earlier was inserted and pressure was applied lightly. Thereafter, heat treatment was performed for 60 minutes in a hot air drying oven at 80°C. The artificial tooth did not come off easily even when pressed hard, and a denture base with the artificial tooth firmly planted was obtained.

Next, apply chloroform to the mouth area of the denture base.
A solution consisting of 100 parts by weight of the polyester carbonate and 1 part by weight of the polyester carbonate was applied with a brush and air-dried for a few seconds.
A solution consisting of 1 part by weight of MH) was applied with a brush and air-dried for several seconds.

A hard backing agent (Cool Liner manufactured by Koh Co., Ltd.) was applied on top of the solution in a conventional manner.

That is, the powder and liquid were mixed, spread evenly on the denture base, and then hardened.

The lining material adhered firmly to the polyethersulfone denture base and was sufficiently durable for practical use.

Comparative Example 2 A hard lining agent was applied to a polyethersulfone denture base in the same manner as in Example 2, except that the solution consisting of chloroform and polyester carbonate and chloroform, polyester carbonate, and polymethyl methacrylate resin was not applied to the denture base. .

The lining was easily removed from the denture base and was unusable.

Effects of the Invention As described above, the present invention provides dental polysulfone resin by using a solution consisting of a chlorinated solvent having a boiling point of 30 to 150°C and an aromatic polyester copolymer or polyester carbonate as an adhesive. This made it possible to firmly bond dental acrylic resin to dental acrylic resin, dramatically expanding the scope of practical use of dental prostheses that combine polysulfone resin and acrylic resin.

[Brief explanation of the drawing]

FIG. 1 is a side view showing an embodiment of an artificial tooth fracture test. 1...Artificial tooth, 1'...Incisal end of artificial tooth, 1''...
...Tooth neck of artificial tooth, 2... Resin base portion, 3... Holder, 4... Artificial tooth tensioning fitting.

Claims (1)

[Claims] 1 An adhesive used to bond dental polysulfone resin and dental acrylic resin, which is made of a chlorinated solvent with a boiling point of 30 to 150°C and an aromatic polyester copolymer or polyester carbonate, and the solvent For 100 parts by weight,
A dental adhesive comprising 0.3 to 20 parts by weight of an aromatic polyester copolymer or polyester carbonate.