JPS6017235B2 - biological hard tissue adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to adhesives for human hard tissues such as teeth and bones.

More specifically, the present invention relates to adhesives that adhere to human tissue under humid conditions, such as adhesives for treating complex fractures, filling materials for fixing artificial joints, tooth adhesives, and tooth filling materials. The present invention is particularly useful for dental applications that require strong adhesive strength under the conditions of use. For room-temperature-curing fillings for teeth and fillings for fixing artificial joints, mixtures of polymethylmethacrynol and methylmethacrynol, and mixtures of pisphenol-A diglycidyl dimethacrynol and triethylene glycol dimethacrynol are used. have been cured by catalytic systems that generate radicals primarily by mixing peroxides and amines in the presence or absence of inorganic fillers.

In this method, the cured product shows almost no adhesiveness to human tissue, and the adhesive strength in a wet state is about 0 to 5k9/m. For this reason, for example, in the case of a cavitary filling for the treatment of cavities, a mechanical retention form called an undercut has been provided in the groove to prevent the filling from falling off after hardening. However, this method has the drawback of removing healthy tooth structure, and since there is no adhesiveness between the filling material and the tooth structure, the margin sealing property is poor (and the problem is that cavities are likely to reoccur). In recent years, adhesives containing cyanoacrylate as a main component have been developed as caries-preventing occlusion agents and orthodontic adhesives for the purpose of adhering to tooth structure. It is said that there are problems with internal durability and operability during use.

Additionally, dental adhesive fillers using trialkylboron as a polymerization initiator have been developed. (Special Public Interest Publication 1977-14)
(No. 318, Japanese Patent Publication No. 45-29195) Although this resin exhibits strong adhesion to tooth dentin, it does not have sufficient adhesion to tooth enamel, which has little organic matter, and the main component of the resin is methacrylic acid. Because methyl is used, it has not yet been fully satisfied as a dental filling material. In addition, it is said that the calcium content of the tooth substance and bond are expected to be produced.
A method has been found that uses vinyl compounds with a phosphoric acid content of 10%.

(Mochiseki No. 51-44152, Journal Dental
(Research No. 35, p. 846) However, this product has a low level of adhesive strength and cannot be said to be sufficient for practical use. Also,
U.S. Pat. ing. However, this one is P
There is a reactivity with the tooth substance, which is thought to be due to the fact that it is a compound having a -F bond, and there is a problem with the safety of the tooth pulp. In view of the above-mentioned problems, the present inventors have determined that the adhesive has the necessary science and engineering properties as a human hard tissue adhesive, such as hardness, compressive strength, water absorption, etc. As a result of intensive research to obtain a human hard tissue adhesive that has excellent adhesion to dentin and enamel, it was discovered that good results could be obtained by adding a compound having a group to the adhesive composition, and the present invention was developed. has been reached.

That is, the present invention provides at least one polymerizable functional group and at least one group (R is R', OR' or N
R'R'', where R' or R'' represents H or an organic residue).

Examples of compounds having a polymerizable functional group and a group used in the present invention include the following.

Necessary scientific and technological properties can be conveniently imparted to these compounds by copolymerizing or mixing them with other polymerizable monomers.

Examples of polymerizable monomers commonly used for this purpose include methyl (meth)acrylele, ethylene glycol di(meth)acrylele, triethylene glycol di(meth)acrylele, bisphenol A di(meth)
Acryleil, Pisphenol A diglycidyl (meth)
Examples include acrylic acid, styrene, pinyl acetate, and maleic acid. It is preferable that these monomers be mixed with the above-mentioned phosphoric acid compound and used as a resin that instantly cures at room temperature. Curing methods used at this time include ultraviolet irradiation, triptylborane catalytic methods, and methods using redox catalysts such as peroxide-amine, but the most effective method is peroxide-amine-catalyzed. It is a three-way catalyst system of sulfuric acid (or its salt) and provides the highest adhesive strength. Note that peroxides include penzoyl peroxide and lauroyl peroxide, and amine compounds include N and N.
-dimethyl-P-toluidine and N,N-diethanol-P-toluidine, and sulfinic acid compounds include benzenesulfinic acid, dodecylbenzenesulfinic acid,
P-toluenesulfuric acid, alkali metal salts or amine salts of these acids, and the like are used. When phosphorus having a group is included in the adhesive composition, the adhesive strength is determined by the amount of phosphorus containing 0.1% (
An improvement was observed when the adhesion strength was higher than 0.3%, reaching the maximum value at around 0.3%, and after that, the adhesion remained almost constant and the lyso content was 1.
If it approaches 0%, it shows a decreasing tendency.

In carrying out the present invention, the compound having the group may be included in the resin body that serves as a filler, or may be used as a primer for hard tissue of a living body and resin.

In the former case, inorganic materials such as quartz powder, glass powder, alumina powder, and polymethyl methacrylate are mixed into the resin to improve the properties of the resin and reduce volumetric shrinkage during polymerization and hardening of the monomers. It is preferable to keep it small. It can also be mixed with metal oxides such as ZNO and Mg○ and used as cement. A part of the OH group of the compound having a group may be substituted with a salt such as ONa, but the degree of salt substitution is such that phosphorus having an OH group is 0.1% or more in the adhesive composition. It should be stopped.

Various metal salts and amine salts are available and are useful for reducing acid irritation to the human body. The present invention will be specifically explained below with reference to Examples.

Example 1 The following two packages were prepared as biological hard tissue adhesives.

Packaging A: Powder - 10 parts by weight of polymethyl methacrylate (molecular weight 13), 1 part by weight of penzoyl peroxide
．． Box weight parts, sodium benzenesulfinate 1. A mixture of neck weight parts.

Packaging B is a liquid formulation containing 8 parts by weight of methylmethac IJ rail, 1 part by weight of ethylene glycol dimethacryleil, 1 part by weight of N-(methacryloxethyl)phosphoric acid monoamide, 1 part by weight of dimethyl-P-toluidine. 0.02 parts by weight of hydroquinone monomethyl ether as a polymerization inhibitor and 2 parts by weight as an ultraviolet absorber
-Hydroxy-4-methoxybenzophenone 0.005
A mixture of parts by weight.

When equal weights of packaging A and packaging B are taken and mixed, the mixture will harden within 3 to 5 minutes at room temperature.

An extracted human tooth was cut into two parts, and on the polished surfaces of each part, a viscous sticky substance prepared by taking equal amounts from both packages A and B and mixing them was applied and fused together. A pongee hole was made in each of the two halves, a lk9 weight was attached, and the piece was immersed in 370 ml of water, and the adhesive remained intact even after 150 days. Example 2 The following two packages C and D were prepared as primers used between tooth filling composite resin and teeth.

Packaging C Liquid. Mix 4 parts by weight of bisphenol A diglycidyl methacrylate, 5 parts by weight of triethylene glycol dimethacryel, 1 part by weight of N,N-jethylstyryl phosphoric acid monoamide, and 1.5 parts by weight of penzoyl peroxide. What I did.

Packaging D Liquid. Parts by weight of bisphenol A diglycidyl methacrylate 4, hydroxyethyl methacrylate 6
parts by weight, 3 parts by weight of sodium benzenesulfinate, N,
A mixture of 2 parts by weight of N-jetanol and P-toluidine.

When C and D are mixed, an adhesive system that firmly adheres to biological hard tissue is activated, and the adhesive hardens within several minutes at room temperature.

Claims (1)

[Claims] 1. There is at least one polymerizable functional group and at least one ▲mathematical formula, chemical formula, table, etc. in the molecule▼ group (R represents R', OR' or NR'R'', R' or R'' is H
or an organic residue). 2. The adhesive according to claim 1, wherein a copolymerizable monomer is added. 3. The adhesive according to claim 1 or 2, wherein a filler is added. 4. The adhesive according to claim 1, 2, or 3, wherein a polymeric curing agent consisting of a peroxide, an amine compound, and sulfinic acid (or a salt thereof) is added. 5. The adhesive according to claim 4, which is packaged in two parts.