JPH0350724B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a dental adhesive that firmly adheres to tooth tissue, particularly dentin. When filling and restoring a cavity created by removing tissue affected by tooth decay or a defective part of a tooth with dental composite resin, an adhesive is applied to the tooth tissue before filling, and the tooth and restoration are bonded and fixed. Treatment methods are becoming more common today. Adhesives used for this purpose include Japanese Patent Publication No. 55-2235 and Japanese Patent Publication No. 58-21607.
It is known that the adhesive containing a phosphate ester monomer disclosed in et al. has excellent adhesive strength with teeth. By using these adhesives in combination with composite resin, the sealability of the boundary between the tooth and the restoration is significantly improved, and clinical problems such as falling off of the restoration, secondary caries, and marginal discoloration are avoided. It has decreased significantly. However, even with the use of this adhesive, this problem did not completely disappear, and stronger adhesives were developed in pursuit of advanced dental treatment.
It is desired that the sealing properties be further improved. In view of the current situation, the inventors of the present invention conducted repeated research aimed at creating an adhesive that adheres even more firmly to teeth, and as a result, they discovered an unexpected fact and arrived at the present invention. That is, in the past, it was generally believed that the presence of water at the bonding interface during bonding between teeth and composite resin inhibits bonding, but the method disclosed in the above patent publication.

[Formula] group or

[Formula] In adhesives containing a polymerizable monomer having a group and a water-soluble polymerization initiator component, by actively adding water to the adhesive, composite resin and teeth (especially ivory) can be bonded together. It was discovered that the adhesion with The present invention, which was obtained based on such knowledge, is based on () at least one molecule in the molecule.

[Formula] Group also teeth

[Formula] A (meth)acrylate polymerizable monomer having a group, () A polymerizable monomer copolymerizable with the polymerizable monomer in (), () (a) Diacyl peroxide, (b) a secondary or tertiary amine bonded to an aryl group and (c)
A dental adhesive comprising a ternary polymerization initiator consisting of an alkali metal salt, an alkaline earth metal salt, or an amine salt of arylsulfinic acid, and () water. within the molecule

[Formula] As the (meth)acrylate polymerizable monomer having a group, Japanese Patent Publication No. 55-2235,
55-5790, 55-24474, 55-30768, JP-A-1987-
Examples include monomers disclosed in Nos. 143372 and 57-164171. In the above publication, these monomers are

【formula】,

【formula】,

【formula】,

【formula】,

[Formula] Although this type of monomer is comprehensively shown, such type of monomer is also widely used in the present invention. Also, in the molecule

[Formula] As a (meth)acrylate polymerizable monomer having a group, the general formula shown in JP-A-58-21607 is [However, R ₁ represents H or CH ₃ and Ra represents a divalent organic group having 4 to 40 carbon atoms. X ₁ and
Y ₁ is O, S or NRb (Rb is H or has 1 carbon
~4 alkyl group). k represents 0 or 1. ] Compounds represented by: In the present invention, when R ₁ is H, it is an acrylate polymerizable monomer, and when R ₁ is CH ₃ , it is a methacrylate polymerizable monomer. The term (meth)acrylate polymerizable monomer is used to refer to both of these. Hereinafter, unless otherwise specified, the notation of (meth)acrylate type will be used with the same meaning.
In addition, it has a structure similar to the above compound, [However, m is an integer from 1 to 4. n is an integer from 2 to 6. R′a is an (m+n)-valent organic group having 5 to 60 carbon atoms. R ₁ , X ₁ , Y ₁ and k are the same as above. ] Compounds represented by the following can also be used. Specific examples of the compounds described above are shown below. In the present invention, these monomers () are used alone or in combination with other polymerizable monomers () that can be copolymerized with the monomers. Other polymerizable monomers used in combination are preferably (meth)acrylic acid derivatives, such as methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl ( meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1 , 6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis[(meth)acryloyloxypolyethoxyphenyl]propane R=H or CH ₃ , t=an integer of 1 to 9], 2,
2'-bis(4-acryloyloxypropoxyphenyl)propane, 2,2'-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (sometimes referred to as Bis-GMA), etc. can be mentioned. The ratio of the polymerizable monomer () to the total monomers [()+()] is preferably 0.5% by weight or more, and if it is less than this, sufficient adhesive strength will not be developed. In the present invention, water is used as a component of the adhesive, and the amount thereof is determined by the polymerizable monomer [()+
()] It is preferably in the range of 10 to 100 parts by weight per 100 parts by weight. When the amount of water added is 10 parts by weight or more, the adhesive strength is significantly improved, but when the amount added exceeds 100 parts by weight, problems arise in the miscibility of the monomer and water. A monomer composition that does not cause phase separation even when 100 weight of water is added is a composition containing a large amount of extremely hydrophilic monomer, for example, a composition containing 50% by weight or more of 2-hydroxyethyl methacrylate. However, adhesives with such compositions are not preferred because they tend to reduce adhesive strength and water resistance. On the other hand, even if the amount of water added is 100 parts by weight or less, phase separation may occur if the monomer is highly hydrophobic. However, in this case, a polar volatile organic solvent such as acetone, methanol, ethanol, etc., with a boiling point of 150°C or lower, preferably 100°C or lower, and capable of dissolving 10% by weight or more of water at room temperature, is added to 100 parts by weight of water. , phase separation can be prevented by adding in an amount of 1000 parts by weight or less. Most of the volatile organic solvent can be easily removed by evaporation by blowing air after applying the adhesive to the tooth surface. By the way, in order to polymerize and cure such monomers with water and obtain the mechanical strength of the cured product sufficient to develop high adhesive strength, it is important to select the polymerization initiator to be used. It's weight. The initiators used in the present invention are disclosed in Japanese Patent Publication No. 56-33363, (a) diacyl peroxide, (b) secondary or tertiary amine bonded to an aryl group, and (c) arylsulfin. alkali metal salts of acids,
It is a ternary initiator consisting of an alkaline earth metal salt or an amine salt. Peroxides used in the present invention include:
Diacyl peroxides such as m-toluoyl peroxide, dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, and dilauroyl peroxide are preferred. Further, as the amine used in the present invention, from the viewpoint of curing speed, a secondary or tertiary amine in which an amino group is bonded to an aryl group is used. For example, N,N-dimethylaniline, N,N-dimethyl-p-toluidine,
N-methyl, N-2-hydroxyethylaniline, N,N-diethanolaniline, N,N-diethanol-p-toluidine, N-methylaniline, N-methyl-p-toluidine and the like are preferred.
The salt of sulfinic acid used in the present invention is preferably a salt of sulfinic acid bonded to an aryl group from the viewpoint of stability, and specifically, sodium benzenesulfinate, sodium p-toluenesulfinate,
Examples include calcium benzenesulfinate, strontium benzenesulfinate, ammonium benzenesulfinate, N,N-dimethyl-p-toluidine benzenesulfinate, and sodium β-naphthalenesulfinate. The adhesive of the present invention is normally packaged in two parts so that the polymerization initiator component is not included in one package, and is supplied to the user, a doctor. It is also possible to separate the adhesive components by a method in which the polymerizable monomer and water coexist in the same package, but in this case, there is a risk that the (meth)acrylic acid ester will gradually hydrolyze during long-term storage. Therefore, it is preferable to separate the two into separate packages. At this time, (a) of the ternary initiators
Diacyl peroxide is packaged in the same package as the polymerizable monomer, and (b) a secondary or tertiary amine bonded to an aryl group and (c) an alkali metal salt, alkaline earth metal salt, or amine of arylsulfinic acid. Preferably, the salt is packaged in the same package as the water. Among the compound group corresponding to the above amine (b), there are many compounds that are poorly or insoluble in water. It is desirable to dissolve the amine and sulfinate in this as a solution. That is,
As a separate packaging method for the constituent components, [monomer composition +
The system of [peroxide]/[water + volatile organic solvent + sulfinate + amine] is most suitable for the present invention. When using the adhesive of the present invention clinically,
First, an adhesive is applied to the tooth surface, and if the adhesive contains a volatile organic solvent, air is blown to evaporate it. A dental composite resin paste is then pressed to bond it to the tooth. Note that the adhesive strength can be enhanced by acid etching the tooth surface in a conventional manner prior to bonding. By using the dental adhesive of the present invention as described above, it is possible to obtain a greatly improved adhesion force to teeth compared to conventional dental adhesives. The adhesive of the present invention has extremely great practical value. The present invention will be explained in more detail by giving examples and comparative examples below. Example 1 A two-component adhesive was prepared according to the following formulation, and this was used to attach a commercially available dental composite resin "ClearFil F" (manufactured by Kuraray Co., Ltd., trade name) to the dentin of a human tooth. The adhesive strength was evaluated by adhesion. Part A Bis-GMA 35 parts by weight 1,4-butanediol dimethacrylate
30 〃 2-hydroxyethyl methacrylate 25 〃 6-methacryloyloxyhexyl 10 〃 Dihydrodiene phosphate benzoyl peroxide 1.5 〃 2,6-di-t-butyl-p-cresol (BHT) 0.05 〃 B liquid 99.5% purity ethanol 60 parts by weight Water 40 Sodium benzenesulfinate 4 N,N-diethanol-p-toluidine 3 The crown of a molar tooth was cut to expose the dentin. After acid etching with a 40% phosphoric acid aqueous solution for 1 minute, a mixture of equal amounts of solutions A and B was applied to the washed and dried dentin surface, and the volatile component ethanol was evaporated using an air syringe. Next, a resin paste of "Clear Fil F" was piled up on the dentin surface coated with adhesive to prepare an adhesive sample. After immersing the five adhesive samples thus prepared in water at 37°C for one day, they were washed at a crosshead speed of 2 mm/min.
When tensile adhesive strength was measured, the average adhesive strength was
It showed an extremely high value of 147Kg/cm ² . Comparative Example 1 A two-component adhesive substantially free of water was prepared according to the following formulation, and its adhesive strength to human tooth dentin was measured by the method of Example 1. Solution A Same as Solution A in Example 1 Solution C 99.5% purity ethanol 100 parts by weight Sodium benzenesulfinate 4 N,N-diethanol-p-toluidine 3 An adhesive prepared by mixing Solution A and Solution C was used. In this case, the average adhesive strength to human tooth dentin was 99 Kg/cm ² . Example 2 A two-component adhesive was prepared according to the following recipe, and a wet ivory rod was butt-bonded using a combination of this and "Clear Fil F" composite resin. D-liquid Bis-GMA 35 parts by weight 1,4-butanediol dimethacrylate
30 〃 2-Hydroxyethyl methacrylate 25 〃 10-methacryloyloxydecyl 10 〃 Dihydrodiene phosphate benzoyl peroxide 1.5 〃 BHT 0.05 〃 Solution B Same as Solution B in Example 1 Two wet ivory 10 x 10 x 40 mm End face of the rod (10×
A mixture of equal amounts of liquid D and liquid B was applied to a 10 mm), and the ethanol was evaporated using an air syringe. Next, the composite resin paste was applied to the adhering surface of one of the ivory rods, and the adhering surface of the other ivory rod was pressed perpendicularly thereon to perform butt bonding. After 30 minutes of adhesion, the sample was immersed in water at 37°C and measured for tensile adhesive strength one day and six months later.
The strength after 2 days is 276Kg/cm ² and after 6 months it is 342Kg/cm ²
It was found that it exhibited extremely high adhesive strength and also had excellent water resistance. Comparative Example 2 A two-component adhesive substantially free of water was prepared according to the following formulation, and its adhesive strength to a wet ivory rod was measured by the method of Example 2. Solution D Same as Solution D in Example 2 Solution C Same as Solution C in Comparative Example 1 When using an adhesive that is a mixture of Solutions A and C, the adhesive strength to the wet ivory rod after one day was 194 Kg/cm ² .
After 6 months, it was 208Kg/ ^cm2 . Example 3 Solutions E and B were prepared according to the following formulations, and their adhesive strength to human tooth dentin was measured according to the method of Example 1. E-liquid Bis-GMA 30 parts by weight neopentyl glycol dimethacrylate
20 〃 2-methacryloyloxyethyl phenyl
50 〃 Hydrodiene phosphate benzoyl peroxide 1.5 〃 2,6-di-t-butyl-p-cresol
0.05 〃 B liquid B liquid of Example 1 The average adhesive strength showed an extremely high value of 120 Kg/cm ² . Comparative Example 3 When the adhesive strength of a combination of Solution E of Example 3 and Solution C of Comparative Example 1 to human tooth dentin was evaluated using the method of Example 1, the average adhesive strength was 78 Kg/cm ² . Example 4 Liquids F and G were prepared according to the following formulation, and their adhesive strength to a wet ivory rod was evaluated according to the method of Example 2. F liquid di(2-methacryloyloxyethyl)
100 parts by weight Hydrodiene phosphate benzoyl peroxide 1.5 〃 G liquid 99.5% purity ethanol 80 parts by weight Water 20 〃 Sodium benzenesulfinate 4 〃 N,N-diethanol-p-toluidine 3 〃 Average adhesive strength is 180Kg/cm ² It was hot. Comparative Example 4 When the adhesive strength of a combination of Solution F of Example 4 and Solution C of Comparative Example 1 to a wet ivory rod was evaluated according to the method of Example 2, it was 130 Kg/cm ² .

Claims (1)

[Scope of Claims] 1 () A (meth)acrylate polymerizable monomer having at least one [Formula] group or [Formula] group in the molecule, () A polymerizable monomer of () A polymerizable monomer that can be polymerized, (a) diacyl peroxide, (b) a secondary or tertiary amine bonded to an aryl group, and (c)
A dental adhesive comprising a ternary polymerization initiator consisting of an alkali metal salt, an alkaline earth metal salt, or an amine salt of arylsulfuric acid, and () water.