JPS6017237B2 - Animal hard tissue adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to adhesives for hard tissues of animals (including humans) such as teeth and bones.

Conventionally, room-temperature instant-curing resins containing methyl methacrylate or bisphenol-A-diglycidyl methacrylate as main components have been used for this purpose, but these resins do not adhere well to the hard tissues of the target animal. The force is extremely weak, and the retention effect based on the mechanical shape of the cured product has been utilized. However, with such a resin, a gap is created between the hard tissue and the hardened resin, resulting in problems such as recurrence of cavities in the case of teeth and loosening of artificial joints in the case of bones. Therefore, the emergence of a resin that truly has adhesive properties with hard tissues has been long awaited. We have previously found that hard structures and strong adhesive properties can be obtained by incorporating a compound with a monobasic acid phosphate group into an adhesive, and have filed a patent application. The present invention was based on the discovery that it provides strong adhesion to tissue and allows convenient curing of the adhesive.

The present invention provides an animal characterized by containing a compound having in its molecule at least one polymerizable functional group and at least one thiophosphoric acid group of a monobasic acid selected from the group consisting of This is an adhesive for hard tissues.

A feature of the present invention is that the above-mentioned compound is contained in the adhesive. Examples of such compounds include the following: These compounds can be used alone, but they can also be used in combination with other polymerizable monomers, and even when mixed in small amounts with other polymerizable monomers, they provide sufficient adhesive strength and provide sufficient adhesive strength. reach your goal. Examples of polymerizable monomers used for this purpose include methyl (
meth)acrylate, ethylene glycol di(meth)acrylate, di- or tri- or tetraethylene glycol di(meth)acrylate, bisphenol A di(
Examples include meth)acrylate, bisphenol A diglycidyl (meth)acrylate, styrene, Q-methylstyrene, (meth)acrylic acid, vinyl acetate, and maleic acid. It is convenient to mix these monopolymers with a compound having a thiophosphoric acid group of a monobasic acid and use the mixture as an instant-curing resin at room temperature.

Curing methods used at this time include an ultraviolet irradiation method, a method using tributylborane as a catalyst, and a method using a redox catalyst. Among those that we have found to be particularly effective are catalysts containing sulfinic acids or salts thereof as constituents. When this catalyst is used, the adhesion between the hard tissues of the human body and the gins becomes even stronger. Among the sulfinic acid compounds, the most preferred are alkali and alkali metal salts, representative examples of which include benzenesulfine salt soda and toluenesulfinate calcium. It is preferable to use these sulfinic acid salts as a ternary catalyst together with a peroxide and an aromatic secondary or tertiary amine in terms of adhesion to hard tissues and curing speed. The adhesive strength of an adhesive containing a thiophosphoric acid group of a monobasic acid is that the content of phosphorus of a monobasic acid is 0.1% (
The effect becomes clear above 0.3%, approaches the maximum value at about 0.3%, and remains almost constant up to about 10%.

If it exceeds 10%, the adhesive strength often tends to decrease.

Note that a part of the OH of the thiophosphoric acid group may be substituted with a salt, but the degree of salt substitution must be maintained such that phosphorus having an OH is 0.1% or more in the adhesive composition. In carrying out the present invention, a compound having a thiophosphoric acid group of a monobasic acid may be contained in the filling material, or it may be contained in a primer that adheres between the hard tissue of the living body and the filling material. You can.

In the case of the former, filling resins are mixed with inorganic materials such as quartz powder, glass powder, alumina powder, polymethyl methacrylate, etc. into the resin to improve the mechanical properties of the cured resin and reduce volumetric shrinkage during curing. It is preferable that In either case, the adhesive is stored in two parts, powder-liquid or liquid-liquid, for stability of the catalyst system, and it is possible to use a method in which the adhesive is cured by mixing. The present invention will be specifically explained below with reference to Examples. Example 1 The following two packages were prepared as a biological hard tissue adhesive.

Packaging A: Powder.

Penzoyl peroxide 1.5% by weight*%, sodium benzene sulfinate 2. Polymethyl methacrylate fine powder with a molecular weight of 13 containing % by weight of . Packaging B: Liquid.

8 parts by weight of methyl methacrylate, ethylene glyco-
Jetanol-P-Toluizine was added to a monomer solution prepared by mixing 1 part by weight of Rudimethacrylate and 10 parts by weight of bis(methacryloxethyl)hydrodiene thiophosphate. % by weight of hydroquinone monomethyl ether 0.
0.02% and 0.005% of 2-hydroxy-4-methoxybenzophenone dissolved therein.

When equal weights of packaging A and packaging B are taken and mixed, the mixture hardens within 395 minutes at room temperature. An extracted human tooth was cut into two parts, and a viscous steel solution prepared by taking equal weights from both packages A and B and mixing them was applied onto the polished surfaces of each part, and the two parts were joined together. Add a weight of lk9 to each of the two parts through the woven holes and make 37
The bond was kept immersed in water at ℃.

The adhesive state was maintained even after 6 months had passed.

Example 2 A set consisting of the following two packages C and D was prepared as a primer for bonding between a tooth and a composite resin for dental restoration filling.

Packaging C: Liquid.

Add 1.5 parts of penzoyl peroxide to a monomer solution containing 4 parts by weight of bisphenol A diglycidyl methacrylate, 4 parts by weight of triethylene glycol dimethacrylate, and 4 parts by weight of 2-methacryloxyethylphenylhydrodiene thiophosphate. % by weight dissolved.

Packaging D: Liquid.

A monomer solution containing 4 parts by weight of bisphenol A diglycidyl methacrylate and 6 parts by weight of hydroxyethyl methacrylate was added with 1% by weight of sodium toluenesulfinate and 2% by weight of N,N-getanol-P-toluidine.
A solution of When equal amounts of packaging C and ○ are mixed, it hardens in a few minutes.

Claims (1)

[Claims] 1 (a) At least one polymerizable functional group in the molecule and (
B) Contains a compound having at least one monobasic acid thiophosphoric acid group selected from the group consisting of ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Adhesive for animal hard tissue. 2. The adhesive according to claim 1, to which a copolymerizable monomer is added. 3. The adhesive according to claim 1 or 2, to which a filler is added. 4. Claims 1 and 2 include a polymerization curing agent consisting of (i) peroxide, (ii) aromatic secondary or tertiary amine, and (iii) sulfuric acid or a salt thereof.
The adhesive according to item 3 or item 3. 5. The adhesive according to claim 4, which is packaged in two parts.