JPH0473403B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a room-temperature curing dental restorative composition that can be used in floor resins, dental cements, adhesives, composites, and the like. BACKGROUND ART As a room-temperature-curing dental restorative composition, one in which a radically polymerizable monomer is combined with benzoyl peroxide and a tertiary amine has been known for a long time. This composition has the drawbacks of being susceptible to discoloration over time due to generated peroxide radicals and tertiary amines, and of insufficient mechanical strength. In order to improve this drawback, proposals have been made to use aromatic sulfinic acid in place of the tertiary amine, and to use aromatic sulfinic acid and/or its salt in combination in addition to peroxide and tertiary amine. . Although this method can prevent the formation of discoloration components caused by peroxides, curing becomes poor due to the influence of moisture and oxygen, and there is a tendency for water absorption and deterioration in the oral cavity. To prevent this, a proposal was made in 1964 to use barbituric acid, heavy metals, and halogens instead of peroxides, which cause discoloration. This composition is said to be free from discoloration and have excellent mechanical strength, but higher mechanical strength and higher adhesiveness between tooth substance and dental metal are required. Problems to be Solved by the Invention Provided is a dental restorative composition that is free from discoloration, has higher strength, and has higher adhesion to dental metal, tooth substance, and dental porcelain. Means for Solving the Problems The present inventor has discovered two cases in which an organic peroxide and a tertiary amine are used together with a barbituric acid and/or a derivative thereof; When using barbiturates or their derivatives together with acid anhydrides, the mechanical strength is improved more than when using barbiturates, heavy metal salts, and/or halogens, and the mechanical strength of dental metals, tooth structure, and dental porcelain is improved. It was found that the adhesion was improved. That is, the present invention provides: A radically polymerizable monomer B the following curing agent (a) organic peroxide (b) aromatic tertiary amine and/or secondary amine (c) barbituric acid or barbituric acid derivative and (d) a dental restorative composition optionally containing an acid anhydride or a phosphate ester. In the present invention, the dental restorative composition is a general term for floor resins, dental composites, dental adhesives, dental cements, and the like. Floor resins refer to floor resins that polymerize at room temperature, repair resins for the same floor resins, and floor resins that can be bonded to metal floors. A dental composite resin containing a composite filling material is shown, and the dental adhesive can be used in conjunction with an orthodontic adhesive, a pit and fissure sealant for preventing caries, and a composite resin restoration. Dental bonding materials, porcelain repair materials, adhesive abutment construction materials that can be bonded to metal posts, metal adhesive resins that can be dissolved in veneers by photopolymerization or heat polymerization, and dental cements for crowns, inlays, Shows resin cements, etc. that are used for onlays, bridges, fixed teeth, etc. In the present invention, the radically polymerizable monomer may be any monomer conventionally used in dental adhesives, cement, floor resins, and composites. Typical monomers include, for example, methyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-(meth)acryloxyethylphosphoric acid, bis(2-(meth)acryloxyethyl)phosphoric acid, ( 2-(meth)acryloxyethyl)phenylphosphoric acid, bisphenol-A-di(meth)acrylate, 2,2'-
Bis((meth)acryloxy-ethoxyphenyl)
Propane, 2,2'-bis(γ-(meth)acryloxy-β-hydroxypropoxyphenyl)propane, neopentyl glycol di(meth)acrylate, mono, di, tri and tetraethylene glycol di(meth)acrylate, di (Methacryloxyethyl)trimethylhexamethylene diurethane and the like can be mentioned. Examples of the organic peroxide used in the present invention include benzoyl peroxide, 4,4'-dichlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and dilauryl peroxide. These peroxides are ingredients that were recognized as having no adhesive properties when used in combination with tertiary amines, but when used in combination with barbiturates,
A new finding was obtained that in the coexistence of tertiary amines, it exhibits strong adhesion to dental metals, tooth substance, and dental porcelain. The amount of peroxide used is per 100 parts by weight of monomer.
The amount is 0.05 to 5 parts by weight, more preferably 0.2 to 3 parts by weight. If the amount is less than 0.05 parts by weight, the room temperature polymerization of the monomer will be insufficient. Moreover, when the amount exceeds 5 parts by weight, the polymerization reaction becomes rapid. In the present invention, a tertiary amine is further used as a curing agent component. The amine may be either an aromatic secondary amine or an aromatic tertiary amine, but an aromatic tertiary amine is preferred in that it rapidly advances curing after a desired period of time. The aromatic tertiary amine and/or the secondary amine have at least one aromatic group on the nitrogen atom, and the aromatic group may have a substituent. Specifically, for example, N-dimethylaniline, N-dimethyl-p-toluidine, N-methyl-N-β-
Hydroxyethyl-aniline, N-di(β-hydroxyethyl)-aniline, N-di(β-hydroxyethyl)-p-toluidine, N-methyl-aniline, N-methyl-p-toluidine and the like are particularly preferred. The amount of these amines used is 0.05 to 5 parts by weight, more preferably 0.2 parts by weight per 100 parts by weight of monomer.
~3 parts by weight. If it is less than 0.05 parts by weight, curing will be insufficient, and if it exceeds 5 parts by weight, it will cause discoloration and, moreover, curing will proceed rapidly, making it impossible to obtain an appropriate working time. Examples of barbituric acid and/or barbituric acid derivatives used in the present invention include barbituric acid, 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 5-phenyl-1-benzylbarbituric acid, Examples include 5-chlorobarbituric acid, 5-nitrobarbituric acid, 2-thiobarbituric acid and salts thereof, particularly alkali metal or alkaline earth metal salts. Particularly preferred barbituric acids or barbituric acid derivatives are 5-butylbarbituric acid and 5-phenyl-1-benzylbarbituric acid. These barbituric acids are preferably used in an amount of 0.01 to 15 parts by weight, particularly preferably 0.1 to 5.0 parts by weight, per 100 parts by weight of the monomer. If it is less than 0.01 part by weight, the polymerization activity will be low, and if it is more than 15 parts by weight, the polymerization reaction will be rapid. In the present invention, an acid anhydride may be further added if desired. Acid anhydrides are useful in that they have the effect of improving adhesion to metals and tooth structure. Examples of suitable acid anhydrides include 4-methacryloxyethyl trimellitic anhydride, 4-acryloxyethyl trimellitic acid, and pyromellitic dianhydride. The amount of acid anhydride used is suitably 30 parts by weight or less per 100 parts by weight of the monomer. More than 30 parts by weight causes a decrease in mechanical performance. Phosphoric acid ester compounds are useful in improving tooth adhesiveness. Preferred phosphoric acid ester compounds are bis(2-methacryloxyethyl)phosphoric acid and (2-methacryloxyethyl)phosphoric acid. The dental restorative composition of the present invention may contain a photopolymerization initiator and a photopolymerization accelerator, if desired. It is useful when the dental restorative composition containing a photopolymerization initiator and a photopolymerization accelerator barbituric acid or a derivative thereof is used in a photopolymerizable form. As a photopolymerization initiator, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin, benzophenone, 2-chlorothioxanthone, 9,10-anthraquinone, camphorquinone, benzyl-4,4
- So-called ultraviolet sensitizers or visible light sensitizers such as dichlorobenzyl and diacetyl are exemplified. As photopolymerization accelerators, dimethyl-p-toluidine, triethylamine, trihexylamine,
Examples include 2-dimethylaminoethanol, N-methyldiethanolamine, and N,N-dimethylaminoethyl methacrylate. It is preferable to use 5 parts by weight or less of each of the photopolymerization initiator and the photopolymerization accelerator based on 100 parts by weight of the polymerizable monomer. The dental restorative composition of the present invention includes adhesives, cement,
It is used for various purposes such as composites and floor resins, but it is combined with fillers and polymer particles depending on the purpose of use. For example, in the case of cement, it is used in two packages: filler (cement powder) and monomer liquid. Fillers for cement include α-quartz powder, strontium glass, barium sulfate, silicon nitride,
Examples include amorphous silica, silica, glass powder, barium glass, polymethyl methacrylate, and polyethyl methacrylate. Among these fillers, inorganic fillers are preferably used after being subjected to surface treatment with a silane compound or the like in advance in order to improve bonding strength with the binder resin. Examples of this silane compound include γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, etc., and 0.1
Coated in an amount of ~20% by weight. Also useful are organic composite fillers obtained by previously kneading and polymerizing these inorganic fillers with monomers and then pulverizing them.
These have a particle size of 0.01 to 200μ or less, more preferably
A suitable value is 0.5 to 60μ, more preferably 0.5 to 30μ. The amount used is 0.3 to 4.2 parts by weight per 1 part by weight of monomer, preferably 0.3 to 4.2 parts by weight per 1 part by weight of monomer.
2.0 to 4.0 parts by weight is suitable. These fillers are mixed with peroxides and barbituric acids to form one packaging unit, and separately blended with monomers and tertiary amines to form a liquid component, and both are stored and sold as a set. When using
It is sufficient to mix both. Of course, the tertiary amine and peroxide may be substituted, but if the tertiary amine and peroxide are mixed in one packaging unit, they will gel, so they should be stored in separate packaging and immediately before use. Allow to mix. Organic composite fillers are also useful as these fillers. When the composition of the present invention is used as a composite, it is also a two-pack set. For example, one package may be a mixture of monomers, fillers, and tertiary amines, and the other may be monomers, fillers, peroxides, barbiturates. Of course, similar to, but not limited to, the cement, the tertiary amine and peroxide should not be mixed in one package. As an embodiment of the present invention, for example, filler, monomer, and tertiary amine and/or aromatic sulfinate are blended in one composite, and filler, monomer, and/or aromatic sulfinate are blended in the other composite.
Peroxide is blended, and a monomer and a barbituric acid derivative are further blended into the adhesive. In this embodiment, the adhesive itself does not cure, but when the adhesive is applied to the cavity of the tooth in advance and then filled with the composite, the peroxide and barbituric acid in the adhesive come into contact with the tertiary amine in the composite. and cure the composite and adhesive. Of course, peroxide may be added to the composite side and tertiary amine may be added to the adhesive side. The binder resin viscosity of the composite is preferably 500 to 100,000 cps, particularly 2,000 to 8,000 cps. The filler used is the same as in the case of cement. It is preferable that the floor resin be packaged in two packages, consisting of a powder composition containing polymer particles and a liquid composition containing monomers. Examples of the polymer particles include polymethymethacrylate, polyethyl methacrylate, and a copolymer of methyl methacrylate and ethyl methacrylate. The particle size of the polymer particles is between 1 and 500μ, preferably
It is 30-300μ. Polymer particles may be a mixture of tertiary amine and barbituric acids, monomers may be a peroxide, or polymer particles may be a combination of peroxides and barbiturates, and monomers may be a combination of a tertiary amine and a barbituric acid. and a tertiary amine may be blended. When the dental composition of the present invention is used as an adhesive, a liquid component containing a monomer, a peroxide, and a barbituric acid and/or a barbituric acid derivative, and a liquid component containing a monomer and a tertiary amine are used. A set consisting of a liquid component containing a monomer and a tertiary amine, and a liquid component comprising a peroxide and a barbituric acid and/or a barbituric acid derivative and/or a salt thereof mixed with an alcohol, etc. It can be used in various forms. This set is used by mixing the two in desired amounts immediately before use. It is also possible to form a liquid component in which a photopolymerization initiator and a photopolymerization accelerator are mixed into these two types of two-liquid components. Examples of the photopolymerization initiator include benzoin methyl ether, benzyl, and camphorquinone, and examples of the photopolymerization accelerator include N-methyldiethanolamine and N,N-dimethylaminoethyl methacrylate. The amount of these photopolymerization initiators and photopolymerization accelerators used is preferably 5 parts by weight or less per 100 parts by weight of monomer. In the present invention, an acid anhydride may be added if desired. Acid anhydrides are useful for further improving the strength and adhesion of cured products. An example of a preferred acid anhydride is 4-acryloxyethyl trimellitic anhydride. The amount of acid anhydride used is 30 parts by weight or less, more preferably 20 parts by weight or less per 100 weight of monomer.
When using an acid anhydride, it is preferable to incorporate it into the package that does not contain the tertiary amine in the set. In the present invention, a phosphoric acid ester compound may be added if desired. Phosphate ester compounds are useful for regulating too rapid polymerization reactions and for further improving adhesion. The amount of the phosphoric acid ester compound used is 30 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the monomer. When using a phosphoric acid ester compound, it is preferable to incorporate it into the package that does not contain tertiary amines in the set. Effects of the Invention The dental restorative composition of the present invention does not discolor over time, and in the case of the conventional BPO-tertiary amine curing agent,
Compared to the combination of barbituric acid and/or barbituric acid derivatives with heavy metals and/or halogens, it is possible to obtain properties such as superior mechanical strength and strong adhesion to dental metals, tooth structure, etc. can. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Examples 1 to 3 and Comparative Examples 1 to 5 The powder agent was mainly composed of silane-treated silica stone and barium sulfate, and contained benzoyl peroxide, 5-phenyl-1-benzylbarbituric acid, 5-butylbarbiturate, and paratoluene sulfate. A sodium fluoric acid salt, 4-acryloxyethyl trimellitic anhydride, and the like were prepared in the formulation shown in Table 1. As a liquid agent, the main ingredients are 2,2'-bis(4-methacryloxyethoxyphenyl)propane and triethylene glycol dimethacrylate, and N,N
-di(β-hydroxyethyl)-p-toluidine,
Dilauryl diethylammonium chloride, butylated hydroxytoluene, etc. were prepared according to the formulation shown in Table-1. In the silane treatment, silica or barium sulfate was treated with γ-methacryloxypropyltrimethoxysilane using a conventional acetic acid method. That is, γ
-methacryloxypropyltrimethoxysilane
A slurry prepared by adding 100 parts by weight each of silica stone or barium sulfate to 100 parts by weight of a solution dissolved in a 0.1% acetic acid aqueous solution to a concentration of 2.0% by weight was air-dried and then heated at 80°C for 2 hours and at 120°C. At
Surface treatment was performed by heat treatment for 30 minutes. Further, the powder/liquid ratio of Examples 1 to 3 and Comparative Examples 1 to 5 was all 3.5:1, and the test items listed in Table 1 were tested. Adhesion tests and strength tests were conducted after the specimens were cured and immersed in water at 37°C for 24 hours.
The bovine teeth used in the bonding test were freshly extracted.
The sample was stored in physiological saline in a refrigerator. As is clear from Table 1, Comparative Examples 1 and 3
Both conventional benzoyl peroxide and tertiary amine and 5-substituted barbituric acid and ammonium chloride systems have relatively slow curing times and are effective for metal-to-metal, enamel-to-metal, and dentin-to-metal bonds. The strength was extremely low, and the mechanical strength was also low. In addition, in the conventional system using benzoyl peroxide, tertiary amine, and para-toluene sulfinate sodium salt in Comparative Example 5, the curing time was 4.2 minutes, and although no retardation effect was observed, the adhesiveness to metal and tooth structure was poor. is low;
In particular, the adhesion force to dentin was zero. In contrast, benzoyl peroxide-tertiary
When using a ternary curing agent in which 5-substituted barbituric acid is added to an amine type curing agent, or in a system in which 4-acryloxyethyl trimellitic anhydride is blended with this ternary curing agent as an acid anhydride, In all cases, superior results were obtained compared to the comparative examples. First, in terms of curing time, Comparative Examples 1 to 4 were from 12 minutes to
The delay was significantly delayed at 120 minutes, whereas in Examples 1 to 3 it was 4 to 4.5 minutes, indicating that the polymerization promoting effect of the ternary curing agent was 3 to 30 times greater, indicating that it had significant catalytic activity. it is obvious. Especially Comparative Example 4-4
- By blending acryloxyethyl trimellitic anhydride, a salt-forming reaction occurs between this acid anhydride and a tertiary amine, and benzoyl peroxide and a tertiary amine form a salt.
Compared to the redox polymerization caused by amines, which was significantly delayed, in Examples 2 and 3, the
A stable curing time of minutes was obtained. Also, comparative example 1
In Examples 1 to 4, the surface of the cured product was significantly inhibited from curing, whereas in Examples 1 to 3, the inhibition was slight. While the cured products of Comparative Examples 1, 2, and 4 exhibited a light brown color, there was no discoloration in Examples 1 to 3. Regarding metal adhesion, Examples 1 to 3 are superior to Comparative Examples 1 to 5. In particular, the results of Example 2 are 230 Kgf/cm ² for Comparative Example 1 and 140 Kgf/cm 2 for Comparative Example 4. An improvement in ^cm2 was observed. The results of Examples 1 to 3 were also superior to Comparative Examples 1 to 5 in adhesion to bovine tooth enamel without acid etching treatment. In particular, the results of Example 3 were 12 times that of Comparative Example 1, and about 5 times that of Comparative Examples 2 and 3.
The adhesive effect was 1.7 times that of Comparative Example 4 and 2.6 times that of Comparative Example 5. In addition, in terms of adhesion to bovine dentin without acid etching, Examples 1 to 3
Sample No. 3 was extremely superior to Comparative Examples 1 to 5. That is, the results of Comparative Examples 1 to 5 are 0 to 2.1 kg.
f/cm ² , whereas the results of Examples 1 to 3 showed
It showed 25.3 to 50.7 Kgf/cm ² , and it became clear that the adhesiveness to dentin was also excellent. especially,
Comparative Example 1 (conventional benzoyl peroxide-tertiary amine system) was 0.5Kgf/cm ² , Comparative Example 3 (conventional 5Kgf/cm 2 )
-Substituted barbituric acid-ammonium chloride system) showed 0 Kgf/ ^cm2 , and Comparative Example 5 (conventional benzoyl peroxide-tertiary amine-p-toluenesulfinate sodium salt system) showed 0 Kgf/ ^cm2. On the other hand, in Example 1, that is, the ternary curing agent of benzoyl peroxide-tertiary amine-barbituric acid derivative system, the curing agent was 50.7 Kgf/cm ²
The dentin adhesion effect was more than 100 times that of Comparative Examples 1, 3, and 5. It was also revealed that the mechanical strength was excellent, and the compressive strength of Comparative Examples 1 to 5 was 1368 to 2168.
Kgf/cm ² was shown, whereas Examples 1 to 3 were 2472
~2525Kgf/ ^cm2 , and in terms of tensile strength, Comparative Example 1
-5 showed 300-415 Kgf/ ^cm2 , whereas Examples 1-3 showed 442-486 Kgf/ ^cm2 , respectively.
These strength properties are due to the excellent polymerization properties of Examples 1 to 3, and this indicates that the benzoyl peroxide-
This may be due to the catalytic activity of the tertiary amine-barbituric acid derivative ternary curing agent or the ternary curing agent-acid anhydride system, which is superior to any of the prior art catalyst systems. It became clear that it was something. Note that many of the excellent properties of Examples 1 to 3 satisfy the requirements for dental restoration composite materials and dental adhesives, such as dental adhesive composite resins and adhesive abutment construction. Applications include metal-adhesive opaque resins for veneers, photopolymerized or heat-polymerized resins for veneers, orthodontic adhesives, and adhesive resin cements for bridges, crowns, inlays, onlays, etc.

【table】

[Table] Example 4 Parts by weight of powder Silane treatment - Silica powder 75.0 Silane treatment - Barium sulfate 24.2 N,N-di(β-hydroxyethyl)-p-toluidine 0.2 5-phenyl-1-benzylbarbituric acid 0.6 liquid Reaction product of 1:2 (mol) of 1,1,3-trimethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate 60 Triethylene glycol dimethacrylate 34.6 Benzoyl peroxide 0.3 4 - Acryloxyethyl trimellitic anhydride thing
5.0 Butylated hydroxytoluene 0.1 Part by weight of pretreatment agent Methyl methacrylate 84.4 Benzoyl peroxide 0.5 4-Acryloxyethyl trimellitic anhydride 15 Butylated hydroxytoluene 0.1 The silane treatment was carried out in the same manner as in Examples 1 to 3 using the acetic acid method. It was done under the conditions. When testing items (1) to (4) below using the above composition,
For liquefaction of powder and liquid, (1), (2) and (4) are 3.5/
1, (3) was tested at 3.8/1. The curing time was about 6 minutes when the powder was liquefied at a ratio of 3.5/1. Thermal cycle test conditions were 1 each for cold water at 4℃ and hot water at 60℃.
1 cycle is immersion for 30 minutes, no cycle is 30 minutes
The durability of the adhesive force was evaluated using cycles of 300 times, 300 times, and 1000 times. (1) Metal-metal adhesion strength (Kgf/cm ² ): The metal used was a Ni-Cr alloy (Shofu Sumaro Nitsukel), which was subjected to aluminum oxide sandblasting and then ultrasonically cleaned for 5 minutes.

[Table] (2) Tooth substance adhesion: Tooth substance using the above powder/liquid (3.5/1)
Table 3 shows the metal adhesion strength (Kgf/cm ² ).

[Table] All the results in the table above are for distilled water at 37°C at 24°C.
These are the measurement results after hours. (3) Proximal sealability: Diameter 3.5 mm, depth 2 on the labial surface of a freshly extracted bovine anterior tooth
After forming a circular box-shaped cavity with a diameter of mm, etching the enamel with a 30% phosphoric acid aqueous solution for 60 minutes, washing with water, drying, and applying a pretreatment agent.
Alternatively, the powder and liquid were mixed at a ratio of 3.8:1 for 1 minute without being applied, and the mixture was filled into the cavity and allowed to harden. After that, the teeth were thermally cycled 1000 times to remove the excess, and then immersed in a fuchsin dye solution at 37°C for 24 hours, cut open, and observed the degree of dye leakage using the above pretreatment agent. case and
In all cases where no dye was used, no dye leakage was observed, and it was found that the margin sealing properties were perfect. In addition, after etching the bovine tooth enamel with a 30% phosphoric acid aqueous solution for 60 seconds, it was sandblasted with aluminum oxide.
Ni-Cr alloy (Smaloy Nitsukel: manufactured by Shofu Co., Ltd.)
When an edge leakage test was conducted using a 100% polyester resin, there was no significant difference between the cases where the pretreatment agent was applied and the cases where the pretreatment agent was not applied, and almost no dye penetration was observed in either case. (4) Porcelain-metal adhesion: Shofu Unibond – Shofu Unimetal (Ni-Cr
Table 4 shows the results of examining the adhesion properties of alloys using the above powders, liquids, and pretreatment agents.

[Table] As shown by the results of test items (1) to (4), the benzoyl peroxide-tertiary amine-barbic acid derivative-acid anhydride system exhibits excellent adhesion to metals, teeth, and porcelain. It became clear that the composition in this example is a dental composite resin, an abutment building material, an orthodontic adhesive,
In addition to adhesive resin cement, it has become possible to demonstrate excellent performance in applications such as porcelain repair materials. Example 5 Powder Part by weight Silanized α-quartz powder 75.0 Silanized barium sulfate 24.2 N,N-di(β-hydroxyethyl)-p-toluidine 0.2 5-butylbarbituric acid 0.6 Part by weight Liquid Bisphenol A di Glycidyl methacrylate 60 Triethylene glycol dimethacrylate 37.6 Benzoyl peroxide 0.3 Bis[(2-hydroxyethyl)methacrylate]
Acid phosphate 3.0 Butylated hydroxyene 0.1 The silane treatment was carried out under the same conditions as in Examples 1-4. When thoroughly kneaded at a powder/liquid ratio of 3.5:1, it hardened in about 30 minutes. Furthermore, the adhesion to bovine teeth without acid etching treatment was good. 37
Table 5 shows the measurement results of adhesive strength after 24 hours in water at ℃.
Shown below.

[Table] Used after sandblasting.
As this example shows, BPO-tertiary amine-
It is clear that the barbituric acid derivative-phosphoric acid compound system also has effective dentin adhesion. Example 6 A Part by weight of agent Silicone oil KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.) 55 Aerosil OX-50 (manufactured by Nippon Aerosil Co., Ltd.) 35 5-Butylbarbiturate benzoyl peroxide 5 5 Part by weight of agent B Bisphenol A diglycidyl methacrylate
18.4 Diethylene glycol dimethacrylate 4.3 Silane-treated α-quartz 75.5 Aerosil R-972 (manufactured by Nippon Aerosil Co., Ltd.) 1.5 N,N di(β-hydroxyethyl)-p-toluidine 0.1 Butylated hydroxytoluene 0.1 The silane treatment was performed as in Example 1. It was carried out in the same manner as in 5. Place A and B in a ratio of 1:2.5 on a paper board,
When thoroughly mixed, it hardened in about 3.5 minutes. Agent A and B
The measurement results of the mechanical strength of the cured product kneaded with the agent were as follows: Compressive strength: 3200 Kgf/cm ² Tensile strength: 525 Kgf/cm ² Bending strength: 1200 Kgf/cm ² Knoop hardness: 70 A The adhesion strength of the mixture of Agent and Agent B to bovine dentin was 60 Kgf/cm ² when measured after 24 hours in distilled water at 37°C. In addition, a cavity with a diameter of 3 mm and a depth of 2 mm was formed on the labial surface of a freshly extracted human tooth, and then the enamel was removed for 30 minutes.
After etching with a % phosphoric acid aqueous solution, washing with water, and drying, a paste prepared by kneading Parts A and B was filled into the cavity. After the paste had hardened, the tooth leakage test specimen from which the excess had been removed was immersed in water at 4°C and 60°C for 1 minute each 1000 times, and then immersed in fuchsin dye solution at 37°C for 3 days. After making an incision and observing the degree of dye leakage, it was found that no dye intrusion was observed, indicating that the margin sealing was excellent. Comparative Example 6 When the A component of Example 6 from which 5-butylbarbituric acid was removed (A' agent) and the B agent of Example 6 were kneaded at a ratio of 1:2.5, the curing time was It took about 15 minutes. The mechanical strength of this cured product was 20 to 30% lower than that of Example 6, and the surface of the cured product suffered from significant polymerization inhibition. When we measured the adhesive strength of a mixture of agents A' and B to bovine dentin, it was found to be 0.6 kgf/
^cm2 , which was a very low result. Furthermore, when a pigment leakage test using freshly extracted human teeth was conducted in the same manner as in Example 6, it was found that pigment penetration was found to be quite deep, and marginal sealing was lacking. Example 7 In conducting tooth adhesion and pigment leakage tests using Agents A' and B of Comparative Example 6, 40 parts by weight of bisphenol A diglycidyl methacrylate, 20 parts by weight of triethylene glycol dimethacrylate, 2- C, in which 0.4 parts by weight of N,N-dimethylamino(β-hydroxyethyl)-p-toluidine and 0.1 parts by weight of hydroquinone monomethyl ether were added to a monomer mixture of 30 parts by weight of hydroxyethyl methacrylate and 10 parts by weight of methyl methacrylate.
Two liquid compositions were prepared: liquid and liquid D, in which 0.6 parts by weight of benzoyl peroxide and 0.8 parts by weight of 5-phenyl-1-benzylbarbituric acid were dissolved or dispersed in ethylene alcohol, and equal amounts of these were prepared. After applying the mixed solution to the tooth surface and evaporating the volatile components with air, we performed the two types of tests mentioned above.The adhesive strength to bovine dentin was determined after being left standing in distilled water at 37℃ for 24 hours. , 55.3 Kgf/cm ² , which was a significant improvement compared to Comparative Example 6. In addition, after forming a cavity of 3 mm φ x 2 mm d in a freshly extracted human tooth, after acid etching, washing with water, and drying, a mixture of equal amounts of the above two components was applied.
After filling and hardening the kneaded paste of equal amounts of A' agent and B agent,
When a dye leakage test was performed and the cavity and the periphery of the cavity wall were observed, almost no dye invasion was observed. Example 8 Powder Parts by weight Polymethyl methacrylate 48.0 Polyethyl methacrylate 50.2 5-phenyl-1-benzylbarbituric acid 1.0 Benzoyl peroxide 0.8 Parts by weight Liquid Methyl methacrylate 85.0 2-Hydroxyethyl methacrylate 10.1 Ethylene glycol dimethacrylate 4.0 Dimethyl- p-Toluidine 0.5 Ultraviolet absorber 0.34 Butylated hydroxytoluene 0.06 The above powder and liquid were mixed at a weight ratio of 1.6/1 and cured in about 5 minutes. Co
- An adhesive test specimen was prepared by applying it to the buffed surface of a Cr-based alloy (Smaroy Cobalt, manufactured by Shofu Co., Ltd.) and hardening it by pressing an acrylic rod with a diameter of 8 mm.
℃, distilled water, measured after 24 hours, 380
An adhesive strength of Kgf/cm ² was obtained. Also, Co-Cr
The above-mentioned powder and liquid were mixed on a metal plate, and after hardening by pressure contact, the mixture was allowed to stand in a fuchsin dye solution at 37° C. for 24 hours, and the degree of dye penetration was observed. As a result, almost no dye penetration was observed. According to this example, a floor resin using the ternary curing agent of benzoyl peroxide-tertiary amine-barbituric acid derivative can have a curing time of up to about 20 minutes by adjusting the formulation. By doing so, we have come to recognize the usefulness of this product as an adhesive floor resin or repair material for metal floors, and as an adhesive for orthodontics. Example 9 Shofu Super Lux Daylight (manufactured by Shofu Co., Ltd.)
40 parts by weight of di(methacryoxyethyl)trimethylhexamethylene diurethane, 2,2'-bis(γ-methacryloxy -β-hydroxypropoxyphenyl)
10 parts by weight of propane, 30 parts by weight of triethylene glycol dimethacrylate, 18.4 parts by weight of 2-hydroxyethyl methacrylate, N,N-dimethyl-p
- A liquid component consisting of 0.5 parts by weight of toluidine, 1.0 parts by weight of N-methyldiethanolamine, and 0.1 parts by weight of butylated hydroxytoluene, 98.0 parts by weight of ethyl alcohol, and 5-butylbarbituric acid.
0.5 parts by weight, 1 part by weight of benzoyl peroxide,
A liquid composition in the form of two liquid components consisting of 0.5 parts by weight of benzyl was prepared, and a cavity of 3 mm in diameter and 2 mm in depth was formed in a freshly extracted human tooth, followed by acid etching treatment, washing with water, and drying. After applying a kneaded solution of equal amounts of the above two liquids and evaporating the volatile components with air, the mixture was filled with Super Lux Daylight, and then photocured by irradiating it with visible light under a Shofu Daylight lamp for 30 seconds. Afterwards, a dye leakage test was performed and the cavity and the margin of the cavity wall were observed, and almost no penetration of the pigment was observed, indicating excellent margin sealing properties.
In addition, using the above two-liquid components, Shofu Super Luxdaleite was inserted and pressure-welded onto acid-etched bovine tooth enamel with 30% phosphoric acid, photocured, and then placed in distilled water at 37°C for 24 hours. The adhesive strength over time was 240 kgf/cm ² . These dye leakage tests and adhesion tests involve immersion in water at 4°C and 60°C.
There was no deterioration after 300 thermal cycles.
It showed excellent durability in tooth adhesion and margin sealing properties. In addition, another two-liquid component was prepared by removing only 5-butylbarbitur from the two-liquid component above,
A test similar to the above was conducted using Shofu Super Lux Daylight. The results showed that pigment leakage reached the dentin and the adhesive strength to acid-etched bovine tooth enamel was 110 Kgf/cm ² . As shown by the above results, the low tooth adhesion and poor margin sealing properties of conventional photopolymerizable composites were improved by the ternary curing agent system containing this barbituric acid derivative.

Claims (1)

[Scope of Claims] 1 A Radical polymerizable monomer B The following curing agent (a) Organic peroxide (b) Aromatic tertiary and/or secondary amine (c) Barbiturate and/or barbiturate A dental restorative composition comprising an acid derivative and (d) optionally an acid anhydride or phosphate ester. 2 The radically polymerizable monomer is methyl methacrylate, 2,2'-bis(methacryloxyethoxyphenyl)propane, 2,2'-bis(γ-methacryloxy-β-hydroxypropoxyphenyl)propane or di(methacryloxy 2. The dental restorative composition according to claim 1, which is ethyl)trimethylhexamethylene diurethane. 3. The dental restorative composition according to item 1, wherein the organic peroxide is benzoyl peroxide or 4,4'-dichlorobenzoyl peroxide. 4. The dental restorative composition according to item 1, wherein the aromatic tertiary amine is N-di(β-hydroxyethyl)-p-toluidine or dimethyl-p-toluidine. 5. The dental restorative composition according to item 1, wherein the aromatic secondary amine is N-methyl-p-toluidine. 6 The barbituric acid or barbituric acid derivative is barbituric acid, 5-butylbarbituric acid,
1,3,5-trimethylbarbituric acid, 5-phenyl-1-benzylzylbarbituric acid, 2-
The first one is thiobarbituric acid or a salt thereof.
The dental restorative composition described in Section 1. 7. For 100 parts by weight of radically polymerizable monomer: (a) organic oxide 0.05 to 5 parts by weight, (b) tertiary amine and 0.05 to 5 parts by weight, (c) barbituric acid and/or its derivatives
2. The dental restorative composition according to claim 1, comprising 0.01 to 15 parts by weight. 8. The dental restorative composition according to item 1, further comprising filler or polymer particles. 9. The dental restorative composition according to any one of clauses 1 to 8, configured to contain the tertiary amine and the peroxide in separate packages. 10. The dental restorative composition according to item 1, wherein the dental restorative composition is an adhesive. 11 Eighth dental restorative composition is a floor resin
The dental restorative composition described in Section 1. 12. The dental restorative composition according to item 8, wherein the dental restorative composition is a cement. 13. The dental restorative composition according to item 8, wherein the dental restorative composition is a composite. 14. The dental restorative composition according to item 8, wherein the dental restorative composition is an adhesive.