JPH0222042B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition for repairing human hard tissue containing a polymerizable monomer and a curing agent, and particularly to a composition for repairing human hard tissue that has good operability and aesthetics. The composition of the present invention can be applied to all hard tissues of the human body such as bones and teeth, and is particularly widely used in the dental field. It is not limited to dental use. Conventionally, cements have been used as dental restorative materials, but recently, acrylic or methacrylic acid polymerizable monomers, curing agents, reaction accelerators, and if necessary, diluents, fillers, and stabilizers have been used. Thermosetting resin compositions are the mainstream in the light range composed of agents and the like. When applying such a composition to dental treatment, appropriate amounts of each component are taken, mixed and kneaded, filled or applied to the affected area, and cured. It is preferable to maintain appropriate fluidity and harden quickly after application.
However, with conventional resin compositions, when the curing properties are good, the curing speed becomes fast, resulting in poor operability; conversely, when the curing properties are good, curing takes a long time, causing pain to patients. In addition to this, there were also defects in that the strength of the composition after curing was low, poor edge sealing properties were caused, and appearance defects such as poor surface condition and discoloration occurred. Various measures have been taken to address the above-mentioned problems, such as adjusting the type and amount of the curing agent and devising the reaction accelerator, but these have not yet been sufficient. The present invention has been made with attention to such circumstances, and uses acrylic acid-based or methacrylic acid-based [hereinafter referred to as (meth)acrylic acid-based] polymerizable monomers,
The purpose of the present invention is to provide a composition for repairing hard tissue of the human body, which is composed of a hardening agent, etc., and is excellent in operability, aesthetics, and margin sealing properties. The gist is that it is composed of a peroxide, an amine, and a sulfonyl hydrazide. The specific configuration of the present invention will be described below. The composition of the present invention necessarily contains a (meth)acrylic acid-based polymerizable monomer and a curing agent, and if necessary, fillers, polymers, stabilizers, etc. are added. The feature of the present invention lies in the composition of the curing agent,
While the conventional curing agent was a two-component system consisting of peroxide and an amine, the present invention uses a three-component curing agent further containing a sulfonyl hydrazide. Peroxides and amines are polymerization initiators and reaction accelerators in general redox systems, and can be freely selected from compounds used in general room-temperature curing reactions, as described below. However, with a two-component curing agent of peroxide and amine, it is difficult to properly adjust both the kneading workability and the time required for curing in the oral cavity, respectively, and by adding sulfonyl hydrazide, these two components can be cured. It has become possible to satisfy both performances simultaneously. That is, although the role of sulfonyl hydrazide in the present invention has not been completely elucidated, although the presence of sulfonyl hydrazide delays the onset of curing or the initial curing speed, the total curing time remains We have now achieved an ideal situation where it does not take too long. Specific examples of each component compound constituting the above composition are as follows. As the sulfonyl hydrazide, alkylsulfonyl hydrazide and arylsulfonyl hydrazide are used, and among them, arylsulfonyl hydrazide is preferable because it is chemically stable, such as P-toluenesulfonyl hydrazide, benzenesulfonyl hydrazide, xylene sulfonyl hydrazide, β-naphthalene Sulfonyl hydrazides and the like are used. As the amine, secondary or tertiary amines are used, and tertiary amines having an aryl group are particularly preferred. For example, N,N'-dimethyl-P-toluidine;N,N'-di(β -Hydroxyethyl)
-P-toluidine; N,N'-dimethylaniline;N-methyl-N'-βhydroxyethyl-aniline; phenylmorpholine and the like are exemplified. Peroxides include benzoyl peroxide, dibenzoyl peroxide, diacyl peroxide, dilauroyl peroxide, di-
Examples include P-chlorobenzoyl peroxide. The content ratio of each component in these curing agents is peroxide:
0.5 to 5 wt%, amine: 0.5 to 4 wt%, sulfonyl hydrazide: 3 to 15 wt%, and in the case of thermal polymerization, peroxide: 0.05 to 1 wt%, amine: 0.05 to 1 wt%, sulfonyl hydrazide: 0.1 to 10 wt%. Each of these is preferable, but of course these values should be adjusted depending on the type of polymerizable monomer and the blending ratio of other compounding agents (diluent, filler, stabilizer, etc.). If the sulfonyl hydrazide content is less than 0.1%, the above-mentioned effects cannot be obtained, and if it exceeds 15%, excess unreacted substances may remain. Next, as the (meth)acrylic acid-based polymerizable monomer used in the present invention, various monomer compounds containing a polymerizable group, such as a vinyl group, are used. In addition to phenol A diglycidyl methacrylate, Examples include 2,2'-bis(4-acryloyloxyethoxyphenyl)propane; 2,2-bis(4-methacryloyloxypropyloxyphenyl)propane, and (meth)propane recently developed by the present inventors. Phosphate compounds that are acrylic acid-based polymerizable monomers, e.g. Examples include the same pyrophosphate compound,
for example etc. are exemplified. Regarding the phosphate compounds and pyrophosphate compounds developed by the present inventors, the viscosity of the compounds themselves is not excessive, and they also have good margin sealing properties when used as dental adhesives, so they can be used as restorative compositions. Particularly effective. Next, auxiliary components that can constitute the composition will be explained. Among these, diluents that can be added when the polymerizable monomer has a high viscosity include low-molecular acrylates and methacrylates, such as methyl methacrylate, ethylene glycol dimethacrylate,
Examples include diethylene glycol dimethacrylate and triethylene glycol dimethacrylate. Fillers include inorganic fillers and prepolymers, and the former include aluminum oxide, silica powder, quartz powder, colloidal silica, glass beads, glass fibers, etc. Those with a particle size of about 1 to 80μ are commonly used, and the composition It increases strength and acts as a filler. The latter contains a small-particle-sized homopolymer or copolymer of the polymerizable monomer, and is added to adjust the viscosity during kneading and to prevent volume shrinkage during polymerization. Other examples of stabilizers include hydroquinone monomethyl ether, tertiary butyl p-cresol, and hydroxymethoxybenzophenone. To obtain the composition of the present invention, the above-mentioned components are suitably divided into two or three parts, mixed and kneaded at the time of application, and applied to the affected area and cured with light or heat (sometimes cured at room temperature). is practical. Examples of such prescriptions include the following. (1) A mixture of a polymerizable monomer and a peroxide is prepared as the A agent, and a mixture of an amine and a sulfonyl hydrazide is prepared as the B agent. Agent A and B during application
The ingredients are mixed and kneaded to obtain a composition. Fillers, stabilizers, etc. may be added to either sachet as necessary. (2) Prepare a mixture of a polymerizable monomer and an amine as agent A, a mixture of a polymerizable monomer and peroxide as agent B, and a polymerizable monomer and sulfonyl hydrazide as agent C, and apply. At the same time, the three ingredients are mixed and kneaded to obtain a composition. Fillers, stabilizers, etc. may be added to any of the sachets as necessary. What must be avoided in such formulations is the packaging of amines and/or sulfonyl hydrazides together with peroxide, as this combination will cause the decomposition of peroxide to proceed during storage of the packaging. . Therefore, if the polymerizable monomer coexists, it will harden in the package, and if it does not exist, curing during application will be inhibited. As mentioned above, when curing by mixing and kneading (meth)acrylic acid polymerizable monomer into a curing agent system consisting of peroxide, amine, and sulfonyl hydrazide, it is possible to improve the kneading operability and to reduce the risk of human health. After application, curing is completed within a short period of time, and a repair material for human hard tissues that is fully satisfactory in terms of affinity and strength to human hard tissues has been provided. The present invention will be explained below with reference to Examples. Example 1 The following composition was prepared and examined for curing speed, discoloration during polymerization, surface curing status, and edge sealing properties. Part A: triethylene glycol dimethacrylate (30 parts by weight), 2-hydroxypropyl methacrylate (10 parts by weight) and dibenzyl peroxide (2 parts by weight) to bisphenol A diglycidyl methacrylate (bis-GMA) (60 parts by weight). (parts by weight) and thoroughly mixed to obtain a uniform dispersion. Agent B: For ethyl alcohol (100 parts by weight),
P-toluenesulfonyl hydrazide (5 parts by weight) and N,N'-di(β-hydroxyethyl)
-P-Toluidine (1 part by weight) was added to obtain a homogeneous solution. A composition obtained by mixing and kneading equal amounts of Part A and Part B was used as investigation samples for each item shown in Table 1. As a comparative example, a composition was prepared using a liquid formulation in which P-toluenesulfonyl hydrazide was not added in the above B composition. The respective results were as shown in Table 1.

[Table] The survey method is as follows. gelation time,
Curing time, discoloration during polymerization, and surface hardening conditions were measured or confirmed by mixing and kneading equal amounts of Part A and Part B and curing the composition in water at 37°C.
In addition, in order to confirm the margin sealability, which is important in the dental field, the degree of pigment penetration was examined using the following method. A grade 3 cavity is created in the extracted tooth using a diamond bur,
A 50% phosphoric acid aqueous solution was applied, and after about 30 seconds, it was washed with water and dried in the air. The above composition was thinly applied to the surface and air-dried again to remove volatile ethanol, and then a kneaded product of a commercially available composite filler material Adapt (manufactured by J&J Company, USA) was filled thereon.
After being left in water at 37°C for 24 hours, it was dipped 100 times at 1 minute intervals into water at 4°C and 60°C colored with fuchsin. The tetrapiece was cut into thin pieces using a cutter, and the degree of penetration of fuchsin into the bonding interface between the tooth and the filling was investigated. Example 2 Fused quartz sand was crushed using a porcelain ball mill to prepare 200 mesh passes. γ-Methacryloyloxypropyltrimethoxysilane in an amount equivalent to 0.5% by weight based on quartz powder was added to a thorium hydroxide aqueous solution with a pH of 9.0 to 9.8, stirred and dissolved, and the above quartz powder was added to this. . When this was thoroughly mixed and stirred, a slurry was obtained. This slurry was dried at 130°C to obtain silane-treated quartz powder. Ethylene glycol dimethacrylate (30 parts by weight) was mixed with bis-GMA (70 parts by weight) to obtain a resin binder. The above quartz powder (80 parts by weight) and colloidal silica (5 parts by weight) were added to this binder (20 parts by weight) and thoroughly mixed to obtain a paste. Divide this paste into two parts, and one part is the paste (100
N,N'-dimethyl-P-toluidine (0.6 parts by weight) and benzenesulfonyl hydrazide (3 parts by weight) were added and thoroughly mixed to obtain a uniform dispersion. Paste (100 parts by weight) on the other side
Add benzoyl peroxide (0.8 parts by weight) to
A uniform dispersion was obtained in the same manner. Equal amounts of this uniform dispersion were mixed and kneaded, and the curing time, discoloration during polymerization, physical properties, etc. were examined, and the results shown in Table 2 were obtained. As a comparative example, a paste containing no benzenesulfonyl hydrazide was used in the above composition.

【table】

[Table] Although the curing time of Example 2 was significantly shortened, the gelation time was not significantly shortened, and the curing time was shortened without adversely affecting operability. The effect of this is extremely remarkable. Signs of improvement can be seen in almost all physical properties of the cured product.

Claims (1)

[Scope of Claims] 1. A composition for repairing hard tissues of the human body containing a (meth)acrylic acid-based polymerizable monomer and a curing agent, characterized in that the curing agent comprises a peroxide, an amine, and a sulfonyl hydrazide. A composition for repairing hard tissues of the human body. 2. The composition according to claim 1, wherein the sulfonyl hydrazide is an arylsulfonyl hydrazide. 3. A composition comprising a filler according to claim 1 or 2.