JPS6346114B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to dental adhesive compositions, and more particularly to dental adhesive compositions that can be used as self-adhesive dental fillings, orthodontic adhesives, etc.
The present invention relates to a dental adhesive composition that can be used as an adhesive that enhances the adhesion between teeth and filling materials such as resin, orthodontic adhesives, and the like. In recent years, composite resins have been developed as an alternative to dental cements such as zinc phosphate cement and silicate cement for the treatment of teeth affected by caries. They are less susceptible to decay and can now be made in colors that are indistinguishable from natural teeth. However, since composite resin does not essentially adhere to tooth enamel and dentin, over a long period of time, gaps may form between the tooth structure and the filled composite resin, causing secondary caries. This can easily result in the composite resin falling off. Conventionally, various adhesion enhancers (adhesive liners) have been developed to improve the adhesion between such composite resins and cavity walls, and adhesive anti-caries filling agents, orthodontic adhesives, etc. Various dental adhesive compositions have been proposed for the purpose of adhering to tooth structure, but many of them have problems such as durability in the oral cavity and operability during use. There are few materials that can strongly adhere to teeth over a long period of time in a humid environment with rapid temperature changes. In view of the above circumstances, the present inventors conducted intensive research on dental adhesive compositions that have strong adhesive strength to teeth, and found that glycidyl methacrylate and aminobenzenedicarboxylic acid or (aminomethyl)
A compound of the following formula (1) obtained by reaction with benzenedicarboxylic acid, (However, R represents a hydrogen atom or a methyl group.)
That is, a product obtained by polymerizing and curing [(2-hydroxy-3-methacryloyloxypropyl)amino]benzenedicarboxylic acids and N-methyl-N-(2-hydroxy-3-methacryloyloxypropyl)aminobenzenecarboxylic acids is dissolved in water. Polymers of the compound represented by formula (1) or copolymers of this compound and other polymerizable monomers can themselves be used as tooth filling materials. It adheres strongly to the tooth wall even when used, so there is no gap formation due to poor adhesion or the filling material falls off, and it also has excellent margin sealing properties when used as a coating or adhesive for fillings such as composite resin. The inventors have found that the present invention is suitable for the purpose of adhesion of tooth substance, as it can significantly improve the quality of the tooth and can effectively suppress secondary caries. That is, the present invention provides a dental adhesive composition in which a polymerizable monomer is polymerized and used, and the polymerizable monomer is represented by the following general formula (1). (However, R represents a hydrogen atom or a methyl group.) A dental adhesive composition characterized in that the compound represented by the following is used alone or as one component is provided. The present invention will be explained in more detail below. The dental adhesive composition according to the present invention is as described above (1).
It contains the compound of formula (1) as a polymerizable monomer alone or as a component together with other polymerizable monomers, and when used, it can be polymerized and cured to form a polymer of the compound of formula (1) or It forms a copolymer etc. with other polymerizable monomers and adheres it to teeth, and it can be used as a tooth filling material, orthodontic adhesive, etc., or as a filling material such as composite resin, etc. For example, it is used as an undercoat (coating agent) as an adhesive to bond orthodontic adhesives etc. to teeth.
Used for the purpose of adhesion to teeth. In this case, the following compounds A to F are preferably used as the compound represented by formula (1). A type 3-[(2-hydroxy-3-methacryloyloxypropyl)amino]phthalic acid represented by; Formula B 4-[(2-hydroxy-3-methacryloyloxypropyl)amino]phthalic acid; Formula C 5-[(2-hydroxy-3-methacryloyloxypropyl)amino]isophthalic acid; Formula D 3-[N-methyl-N-(2-hydroxy-3-methacryloyloxypropyl)amino]phthalic acid; E formula 4-[N-methyl-N-(2-hydroxy-3-methacryloyloxypropyl)amino]phthalic acid; Formula F 5-[N-methyl-N-(2-hydroxy-3-methacryloyloxypropyl)amino]isophthalic acid. In addition, in the present invention, one of the compounds of formula (1) above
Only the seeds may be used, or two or more types may be used in combination. In the present invention, the compound of formula (1) is contained alone or together with other polymerizable monomers in a dental adhesive composition, and is polymerized and cured during use. The other components of the dental adhesive composition of the present invention vary depending on the type of adhesive composition, purpose of use, etc., but known components that are normally blended depending on the type, purpose, etc. can be used. For example, when used as an adhesive filler, only the compound of formula (1) is used as a polymerizable monomer, and by polymerizing and curing it in the presence of a curing agent, it can be used as an adhesive filler. However, usually a method is adopted in which the compound of formula (1) is mixed with other polymerizable monomers and polymerized and cured in the presence of a curing agent at the time of use. In this case, other polymerizable monomers include methyl methacrylate, hydroxyethyl methacrylate, ethylene glycol di-methacrylate, di- or tri- or tetraethylene glycol di-methacrylate, glycidyl methacrylate, 2,2'-
Bis(methacryloxyphenyl)propane, 2,
2'-bis[4-(3-methacryloxy)-2-hydroxypropoxylphenyl]propane, styrene, 1,3-butanediol dimethacrylate,
Tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, bisoxyethylated bisphenol A diacrylate, etc. may be blended. In addition, viscosity, curing speed,
In order to control polymerization shrinkage, etc., a polymer or oligomer of a polymerizable monomer containing the compound of formula (1) is blended, and an inorganic filler such as silica, glass beads, alumina, or quartz powder (preferably with a particle size of 100 μm or less) is added. or those treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, or vinyltrimethoxysilane to improve bonding with the resin, and cured agent, polymerization inhibitor, colorant, antioxidant,
Desired ingredients such as ultraviolet absorbers may also be used. In addition, when using a combination of amine and peroxide, or p-toluenesulfinic acid and peroxide, etc. as a curing agent, if only the compound of formula (1) is used as the polymerizable monomer, Divide this into approximately two equal parts, add one curing agent such as amine or p-toluenesulfinic acid to one half, add the other curing agent such as peroxide to the other, and add the other polymerizable monomer ( 1) If the compound of formula is used by mixing,
Similarly, this other polymerizable monomer is divided into approximately two equal parts, one of the curing agents is added to one of the two, and the other curing agent is added to the other, and the compound of formula (1) is added to one of the two halves. Alternatively, it is preferable to manufacture by mixing both of them (these are used by mixing them at the time of use). In this case, other components are also mixed into one or both of them. Further, in the case of using an ultraviolet sensitizer and curing with ultraviolet rays, it can be produced by mixing all the necessary components. In this case, the amount of the compound of formula (1) is not particularly limited, but if the other polymerizable monomer is used, it is 1 to 30% based on the other polymerizable monomer.
(% by weight, the same applies hereinafter), particularly preferably from 2 to 15%. If it is less than 1%, the adhesion effect will be poor;
Also, if more than 30% is added, the hardness of the cured product may decrease. It is preferable that the amount of the polymerizable monomer is 10 to 45% of the total composition, and the amount of the inorganic filler is 55 to 85% of the total composition. In addition, when the composition of the present invention is used as an adhesive for bonding a tooth and a conventional filling such as a composite resin, the composition of formula (1) is added to an organic solvent such as ethanol, ethyl ether, or chloroform. It can be produced by containing the compound at 1 to 15% of the total, and it can also be produced by containing the compound of formula (1) in the other polymerizable monomers at 1 to 15% of the total. You can. Furthermore, it can also be manufactured and used in the same formulation as the filler. Note that if the content of the compound of formula (1) is too small or too large, it will be difficult to obtain an adhesive effect. The dental adhesive composition of the present invention is cured and used depending on its type, purpose, etc. For example, when used as a filler, the adhesive composition (filler) is filled into the cavity to be filled, When hardened and used for bonding between a dental filling and a tooth, the adhesive composition is applied to the cavity wall, for example after cavity formation;
Next, it is used by filling with a predetermined filler, curing, or the like. Thus, in the dental adhesive composition of the present invention, the polymer of the compound of formula (1) has good adhesiveness to tooth substance, and maintains high adhesive strength even in water or saliva. Therefore, it has good durability in the oral cavity,
For example, when used as a filling material, it firmly adheres to teeth for a long period of time even in environments that are humid and subject to rapid temperature changes, such as the inside of the oral cavity. When used as an undercoat (varnish) for adhesion purposes, it not only firmly adheres to teeth, but also strongly adheres to composite resins, orthodontic adhesives, etc., and therefore does not cause gaps to form between it and the teeth. It is reliably prevented, the margin sealability is improved, and the prevention of secondary caries is achieved. Hereinafter, the present invention will be specifically explained with reference to Examples. In addition, in the following examples, all parts indicate parts by weight. [Example 1] Compounds A to F described above were each dissolved in ethanol at a concentration of 5% to prepare a coating agent (dental adhesive composition). Next, the surface of the bovine tooth filled with plaster in the holder and the 6 mmφ x 40 mm acrylic rod were polished to a certain level of smoothness using a polisher, and then the smooth surface of the bovine tooth was treated with 3M phosphoric acid for 30 seconds, washed with water for 30 minutes, Dry with compressed air. Next, the coating agent was applied to the dried tooth surface, and after drying, the acrylic rod was adhered using an adhesive having the following formulation. The adhesive strength of the samples stored in artificial saliva at 37°C for 14 and 60 days was measured using a strograph (pulling speed: 5 mm/min). The results are shown in Table 1. Adhesive formulation: (a) Methyl methacrylate polymethyl methacrylate N,N-dimethyl-p-toluidine 2 parts 0.4 parts 0.04 parts (b) Methyl methacrylate polymethyl methacrylate benzoyl peroxide 2 parts 0.4 parts 0.04 parts (a) and (b) at a weight ratio of 1:1.

[Example 2]

10 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, bisphenol-A
- 50 parts of diglycidyl methacrylate and 350 parts of silane-coupled quartz powder with a particle size of 50 μm or less were thoroughly mixed and divided into two equal parts. On the other hand, 3-[(2-hydroxy-3-methacryloyloxypropyl)
6 parts of amino]phthalic acid (the above compound A) and N,
After adding 2 parts of N-dimethyl-p-toluidine and adding 2 parts of benzoyl peroxide to the other, the two were mixed. Using this material, we adhered the smoothed bovine tooth surface to an acrylic rod in the same manner as in Example 1, and measured the adhesion force using a strograph.The adhesive strength was 83 kg/cm ² on average after being stored in water for one week. The adhesive strength was shown. In addition, when using compounds B to F, each
76Kg/cm ² , 64Kg/cm ² , 78Kg/cm ² , 76Kg/cm ² , 80
It showed an adhesive strength of Kg/ ^cm2 . [Example 3] A diameter of 4 mm and a depth of 2 to 2.5 mm on the labial surface of an extracted human tooth.
A cavity was formed and the cavity wall was etched with 3M phosphoric acid for 30 seconds. Next, 3-[(2-hydroxy-
After applying a thin layer of a solution consisting of 10 parts of 3-methacryloyloxypropyl)aminophthalic acid (compound A), 60 parts of methyl methacrylate, and 30 parts of tetraethylene glycol dimethacrylate to the cavity wall, Adaptake (manufactured by Jyonson & Jyonson) was applied. (product name) was filled. Thirty minutes after filling, it was stored in water at 37°C, and one day later, a percolation test was conducted in which it was immersed in fuchsin aqueous solutions at 4°C and 60°C 60 times for 1 minute alternately to test its margin sealing properties. The extracted tooth was cut at the center and examined for the presence of pigment (fuchsin) intrusion between the cavity wall and the filling, but no pigment intrusion was observed, and good results were obtained. Similar results were also shown for compounds B, C, D, E, and F. On the other hand, in the case where the adapter was directly filled without treatment with a solution containing compounds A to F, the pigment (fuchsin) penetrated into the cavity wall dentin or the cavity floor, and therefore the composition of the present invention did not interact with the tooth. It was also found to be effective in adhering both fillers.

Claims (1)

[Scope of Claims] 1. In a dental adhesive composition that is used by polymerizing a polymerizable monomer, the polymerizable monomer has the following general formula:
(1) (However, R represents a hydrogen atom or a methyl group.) A dental adhesive composition characterized in that the compound represented by the following is used alone or as one component. 2 The compound represented by formula (1) is 3-[(2-hydroxy-3-methacryloyloxypropyl)amino]phthalic acid, 4-[(2-hydroxy-3-methacryloyloxypropyl)amino]phthalic acid,
5-[(2-hydroxy-3-methacryloyloxypropyl)amino]isophthalic acid, 3-[N-
Methyl-N-(2-hydroxy-3-methacryloyloxypropyl)amino]phthalic acid, 4-
selected from [N-methyl-N-(2-hydroxy-3-methacryloyloxypropyl)amino]phthalic acid and 5-[N-methyl-N-(2-hydroxy-3-methacryloyloxypropyl)amino]isophthalic acid Claim 1 which is
The dental adhesive composition described in Section 1.