JPH0629164B2 - Dental restorative composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dental restorative composition having adhesiveness.
More specifically, the present invention shows excellent aesthetics due to the characteristics of a curing agent, and a dental adhesive that firmly adheres to enamel and dentin of natural teeth and various metal materials, ceramic materials, a floor resin, The present invention relates to a restorative composition such as coposit resin, cement, and resin for veneering crown.

The composition according to the present invention can also be applied to the field of human hard tissue adhesives and general industrial adhesives.

2. Description of the Related Art As a dental restorative resin, many studies have been conducted on (meth) acrylic monomers because of their advantages of good aesthetics and being able to cure in a short period of time, and those with excellent properties are provided. Has been done. For example, US Pat. No. 30,661.
No. 12, No. 3,629,187, and Japanese Patent Laid-Open No. 4
8-11156 and Japanese Patent Publication No. 48-103648
Japanese Patent Laid-Open Publication No. 2003-242242 discloses a resin which is cured by a redox polymerization method, an ultraviolet polymerization method or a visible light polymerization method using a polymerization initiator and an accelerator, and contains an aromatic polyfunctional acrylate or methacrylate or a urethane modified product thereof as a main component. As a dental composite resin, an adhesive, a pit fissure sealing material, and the like are disclosed.

In the recent field of dentistry, in place of conventional methylmethacrylate-based instant polymerization resins, the above binder resins, particularly methacrylic monomers as the main component, abbreviated as BIS-GMA resin, have been used. A viscous composite material containing a large amount of inorganic filler is provided as a composite resin.

However, this type of dental composite resin generally has insufficient adhesion to the tooth structure, so the restoration may fall off, and secondary caries and pulp irritation caused by the invasion and leakage of bacteria etc. at the peripheral edge of the adhesive. Edge crushing and edge coloring occur, which is a dental clinical problem.

In order to solve such clinical problems, a method of improving the adhesiveness between the composite resin and the tooth substance has been attracting attention.

For example, a so-called acid etching method of treating enamel with an acid has been known for a long time [Journal of Dental Research, No. 3].
4 (6), pp. 849-853 (1955)]. The adhesion by this method is not due to the chemical bond between the tooth substance and the binding resin, but the mechanical intrusion is caused by hardening and mooring of the resin that has penetrated into the microstructure formed mainly by the decalcification of the enamel trabeculae. It has been found that the marginal leakage test does not provide sufficient marginal sealing performance because of the fact that it is based on

It has also been proposed to increase the adhesiveness between the resin and the tooth substance by using methacrylic monomers containing a phosphoric acid ester residue or an acid anhydride residue. The redox hardeners (benzoyl peroxide and tertiary
Depending on the amine, the curability may be poor, or the adhesiveness may be insufficient due to a salt forming reaction, and sufficient adhesiveness may not be exhibited even when used in combination with other known curing agents.

On the other hand, the recent trend of research on dental resins has shifted to the development of resins showing excellent adhesiveness not only to the tooth substance but also to various metals and ceramic materials. However, these disclosed prior arts cannot be said to have sufficient adhesiveness to the adherend, and it is recognized that there is a serious defect in the conventional curing agent component as a factor of this.

Benzoyl peroxide and aromatic third compounds have been used as radically polymerizable monomers that have long been known as dental restorative compositions.
A composition containing an amine as a curing agent tends to discolor over time due to ultraviolet rays, heat, etc. due to a product formed from an intermediate product by the reaction of two components of the curing agent, and has insufficient mechanical strength. Not only that, but it also has low adhesion to tooth and metal (about 0.5-0.6Kgf / for dentin without acid treatment)
cm ² ).

In addition to the above-mentioned curing agent system containing benzoyl peroxide and aromatic tertiary amine, 4-methacryloxyethyl trimellitic anhydride (JP-A-54-11149 and JP-A-54-1149).
Nos. -12338 and 55-110171) are mixed, the redox is caused because the charge transfer complex is rapidly formed immediately after mixing between the aromatic tertiary amine and the acid anhydride residue. Polymerization is significantly delayed,
The cured product turns yellowish brown and has low adhesiveness.

In addition to the above curing agent system containing benzoyl peroxide and an aromatic tertiary amine, CH ₂ ═CH—P (OH) ₂ or CH _{2
= CH-C 6 H 4 -CH} 2 PO (OH) radical polymerizable organic phosphorus compounds such as ₂ (Journal of Dental Research,
53, 878-888, and 56
Vol., Pp. 543-952), the polymerization is significantly delayed or does not cure,
The expected adhesiveness cannot be obtained.

The composition containing peroxide and aromatic sulfinic acid as a curing agent solves the problem of discoloration, but not only does not achieve sufficient curing due to the influence of moisture and oxygen, but the cured product contains Due to the hygroscopicity of the residual sulfinic acid, water absorption in the oral cavity tends to be high, causing white spots and deterioration.

Japanese Patent Publication No. Sho 56-33363 discloses a technique for improving the curing rate of a resin and the adhesion to tooth structure by adding a metal salt of diacyl peroxide, an aromatic tertiary amine and an aromatic sulfinic acid as a curing agent. Is disclosed. However, in this case, since the aromatic sulfinate has poor solubility in the radical-polymerizable monomer, the mechanical strength of the cured product is increased by the presence of the salt precipitated during the polymerization of the system and the insoluble residual hardener component. And the water resistance and adhesiveness in the oral cavity are reduced.

JP-B-42-14318 and 45-2919
Japanese Patent Publication No. 5 discloses a technique of improving the adhesiveness to dentin, particularly dentin, by using trialkylborane as a hardening agent.
For example, tri-n-butylborane can be used only in combination with a very limited radically polymerizable monomer such as methyl methacrylate, and has a problem of storage and clinical safety due to its ignition property. There is also a difficulty in sex.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention solves the above-mentioned problems of the prior art, has high safety in clinical operation, is excellent in aesthetics without discoloration, and has only enamel or dentin of natural teeth. In order to provide a novel dental restorative composition showing a high adhesiveness to various metal materials, ceramic materials, etc. in combination with a radically polymerizable monomer and a curing agent Is.

Means for Solving the Problems The dental restorative material composition of the present invention comprises a radically polymerizable monomer and a curing agent, but is particularly characterized by the curing agent. That is, if a combination of (a) organic sulfinic acid amide, (b) organic peroxide, (c) organic acid, acid anhydride or phosphoric acid ester is used as a curing agent, the cured product does not discolor, and the aesthetic effect is obtained. The present invention has been accomplished by discovering that it has excellent properties and strongly adheres to tooth enamel and dentin as well as metal and porcelain.

The feature of the present invention resides in the constitution of the hardener, which is the hardener used in the conventional dental resin, which is a combination of benzoyl peroxide and a tertiary amine, an organic peroxide and a tertiary amine, and Whereas the metal salt of aromatic sulfinic acid was used in combination, or the alkylboron derivative, it consisted of the following combinations: (a) organic sulfinic acid amide (b) organic peroxide (c) organic The use of a combination of acids, acid anhydrides or phosphoric acid esters.

Radical polymerizable monomer and the above curing agent system (a), (b),
The composition of the present invention containing (C) has no discoloration and is excellent in aesthetics,
Moreover, since it has a strong adhesive property to tooth structure, metal and porcelain, it is very effective as a dental restorative composition.

Hereinafter, the present invention will be described in more detail. In the present specification, "floor resin" means a floor resin, a repair resin, a floor lining material, and a floor resin that can be bonded to a metal floor. , "Dental composite resin" means a dental composite resin and an abutment, etc. in which an inorganic filler or an organic composite filler is contained in the composition,
"Dental adhesives" are orthodontic adhesives, pit and fissure sealing materials to prevent erosion, dental bonding materials that can be used together with composite resin restorations, pretreatment primers, photopolymerization or heat polymerization methods. Means a metal adhesive resin and porcelain repair adhesive that can be used in combination with a veneering crown resin, and "dental cement" means backing lining cement and crown, inlay, onlay, bridge and rocking tooth fixing Means resin cement, etc. applicable to
Further, the "resin for dental front cover" means a baking hard resin by a heat polymerization method, a photopolymerization hard resin and the like.

Furthermore, "(meth) acrylate" means acrylate or methacrylate, and "organic acid" means an organic acid other than a barbituric acid derivative.

The radically polymerizable monomer used in the present invention, conventionally, floor resin, dental composite resin,
In addition to radical-polymerizable monomers used in dental restorative materials such as dental adhesives, resin cements, and veneering crown resins, radical-polymerizable monofunctional and 2- to 4-functional acrylates and Examples thereof include methacrylates. These (meth) acrylates may have a fluorine atom, an aryl group or a urethane bond in the molecule.

Such compounds include the following: methyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, t.
-Butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (p
-Methyl) phenoxypropyl methacrylate, neopentyl glycol di (meth) acrylate, monoethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, dodeca Ethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, bisphenol A-di (meth) acrylate, 2,
2'-bis [(meth) acryloxy-ethoxyphenyl]
Propane, 2,2'-bis [(γ- (meth) acryloxy-
β-hydroxypropoxy) phenyl] propane, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycidyl (meth) acrylate, t-butylamino-ethylmethacrylate HF salt, methyl-α-fluoroacrylate, 2,2,2-trifluoroethyl methacrylate, 2,
2,2-trifluoroethyl-α-fluoroacrylate, urethane bond-containing compound is a reaction product of diisocyanates and hydroxyl group-containing (meth) acrylate, and molar ratio of diisocyanates and hydroxyl group-containing mono (meth) acrylates. Reaction product of 1: 2, reaction product of diisocyanates and hydroxyl group-containing di (meth) acrylate in a molar ratio of 1: 2, diisocyanate, hydroxyl group-containing mono (meth) acrylate and hydroxyl group-containing di (meth) ) Reaction product with acrylates in a molar ratio of 1: 1: 1, diurethane prepolymer having diisocyanate groups at both ends and a hydroxyl group-containing mono (meth) acrylate in a molar ratio of 1: 2
Reaction product of the urethane prepolymer and the hydroxyl group-containing di (meth) acrylate in a molar ratio of 1: 2, the urethane prepolymer and the hydroxyl group-containing mole (meth) acrylate and the hydroxyl group-containing Reaction products with a molar ratio of 1: 1: 1 with di (meth) acrylates, such as di ((meth) acryloxyethyl) xylene diurethane, di ((meth) acryloxyethyl) toluene diurethane, di ((( (Meth) acryloxyethyl) hexamethylenediurethane, di ((meth) acryloxyethyl)
Trimethylhexamethylene diurethane, di ((meth) acryloxyethyl) isophorone diurethane, bis [di
((Meth) acryloxy) glycerol] hexamethylenediurethane, bis [di ((meth) acryloxy) glycerol] trimethylhexamethylenediurethane, bis [di
((Meth) acryloxy) glycerol] isophorone diurethane, etc., with a molar ratio of 1: 1: 1: 1,1,3-trimethylhexamethylene diisocyanate, 2-hydroxyethyl (meth) acrylate and glycerin di (meth) acrylate. The reaction product, a reaction product of isophorone diisocyanate, 2-hydroxyethyl (meth) acrylate and glycerin di (meth) acrylate at a molar ratio of 1: 1: 1, and a molar ratio of (meth) acrylic acid and glycidyl methacrylate at a ratio of 1 :. Reaction of a reaction product of 1 with a reaction product of 1,1,3-trimethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate with a glycidyl methacrylate of 1: 1 in a molar ratio of 1: 1: 1. Product, 2-hydroxyethyl methacrylate and glycy Reaction product with a molar ratio of 1: 1 and isophorone diisocyanate, a reaction product with a molar ratio of 1: 1 and a reaction product with (meth) acrylic acid and glycidyl methacrylate with a molar ratio of 1: 1. To diphenylmethane diisocyanate in a molar ratio of 1:
The reaction product of No. 1 is exemplified.

The organic sulfinic acid amide used in the present invention has the following formula: (In the formula, R represents an aliphatic or aromatic residue which may have a substituent such as a halogen atom, an alkyl group, an alkoxy group or an aryl group, and R ′ and R ″ may be the same or different. , Each independently represent a hydrogen atom, a lower alkyl group or an aryl group, or constitute a heterocyclic residue together with a nitrogen atom).

Aromatic sulfinic acid amide is a particularly suitable sulfinic acid amide in that it has high solubility and activity for the above-mentioned radically polymerizable monomer, is easy to manufacture, and has good storage stability. Examples of compounds include: benzenesulfinic acid amide, p-toluenesulfinic acid amide, p-chlorobenzenesulfinic acid amide, N, N-
Dimethyl-benzenesulfinamide, N, N-dimethyl-p-toluenesulfinamide, N, N-methyl-
Phenyl-benzenesulfinic acid amide, N, N-dimethyl-p-chlorobenzenesulfinic acid amide, benzenesulfinic acid morpholide, p-toluenesulfinic acid morpholide, p-chlorobenzenesulfinic acid morpholide, benzenesulfinic acid piperidide, p-chlorobenzene Sulfinic acid piperidide, N, N-dimethyl-β-naphthalene-sulfinic acid amide, methanesulfinic acid anilide, methanesulfinic acid-p-toluidide and the like. Among these exemplified compounds, particularly preferable ones are p-toluenesulfinic acid morpholide, N, N-dimethyl-p-toluenesulfinic acid amide, benzenesulfinic acid molylide and N, N-dimethyl-benzenesulfinic acid amide.

If desired, two or more organic sulfinic acid amides may be used in combination.

The compounding amount of the organic sulfinic acid amide is about 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the radical-polymerizable monomer. If it is less than 0.01 parts by weight, the intended purpose of the present invention cannot be achieved, and if it exceeds 20 parts by weight, the polymerization reaction is excessively promoted, which causes deterioration of the cured product.

Examples of the organic peroxide used in the present invention include the following compounds: benzoyl peroxide, 4,4'-dichlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dilauryl peroxide, methyl ethyl ketone. Peroxide, t-butyl peroxymaleic acid, succinic acid peroxide and the like. Among these peroxides, particularly preferable ones are represented by the following general formula (However, in the above formula, R is an alkyl group having 1 to 3 carbon atoms), and a half-perester of a bifunctional acid is preferably used. A particularly preferred organic peroxide is t
-Butylperoxymaleic acid, benzoyl peroxide, 4,4'-dichlorobenzoyl peroxide.

If desired, two or more organic peroxides may be used in combination.

The blending amount of the organic peroxide is about 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight based on 00 parts by weight of the radical-polymerizable monomer.
Parts by weight. If it is 0.01 part by weight or less, the polymerization reaction is insufficient, and if it is 10 parts by weight or more, the polymerization reaction is excessively promoted.

Further organic acid as a constituent of the curing agent in the present invention,
An acid anhydride or phosphoric acid ester is used. The combination of only the organic sulfinamide and the organic peroxide has a problem that the curing time is long because it does not cure or the curing speed is slow. Further, a combination of only the organic sulfinic acid amide and the organic acidic component has the same problem. On the other hand, in a conventional curing agent system using an organic peroxide and a tertiary amine, the curing rate is delayed by adding an acidic component. But,
In the present invention, the addition of an acidic component such as an organic acid, an acid anhydride or a phosphoric acid ester accelerates the curing rate, gives an appropriate curing time, and greatly contributes to the improvement of adhesion.

As the organic acid used in the present invention, general mono-, di-,
Although tri-, tetra-carboxylic acids and sulfonic acids can be used, a suitable organic acid is a radical polymerizable monomer having a carboxyl group in one molecule. For example, methacrylic acid, acrylic acid, 4-methacryloxyethyltrimet acid, 4-acryloxyethyltrimet acid, 6-methacryloxyethylnaphthalene 1,2,6-tricarboxylic acid, N, O-dimethacryloxytyrosine, Examples thereof include o-methacryloxytyrosine, N-methacryloxyphenylalanine, and 1,4-dimethacryloxyethylpyromellitic acid.

Next, as the acid anhydride, a radical polymerizable monomer having an acid anhydride group bonded to an aryl group is preferable due to its structure. Suitable acid anhydrides include 4-methacryloxyethyltrimet acid anhydride, 4-acryloxyethyltrimet acid anhydride, 6-methacryloxyethylnaphthalene 1,2,6-tricarboxylic acid anhydride and 6-methacryl anhydride. Roxyethylnaphthalene 2,3,6-tricarboxylic acid anhydride, 4-methacryloxyethoxycarbonylpropionoyl 1,8-naphthalic acid anhydride, 4-methacryloxyethylnaphthalene 1,8,4-tricarboxylic acid anhydride, etc. It is illustrated.

Conventionally, when a monomer containing an acid anhydride group is used in combination with a curing agent system of benzoyl peroxide and an aromatic tertiary amine, for example, C-T is rapidly added in the composition immediately after mixing. A complex-forming reaction occurred, the cured product exhibited a yellowish brown color, the curing time was delayed, and the adhesive strength was low. However, the present inventors, by using these acid anhydrides in combination with an organic peroxide and an organic sulfinic acid amide, the curing rate becomes stable, there is no yellow brown discoloration, enamel and dentin of natural dentin, It has been found that it adheres strongly to metals, ceramics, etc.

Next, the phosphoric acid ester may be any radical-polymerizable monomer having a phosphoric acid ester group in one molecule. Examples thereof include (2- (meth) acryloxyethyl) phosphoric acid, (2 (meth) acryloxyethyl) phenylphosphoric acid, and bis (2- (meth) acryloxyethyl) phosphoric acid.

Conventionally, these phosphoric acid esters had a problem that the polymerization was significantly delayed or they were not cured when used in combination with a curing agent system using benzoyl peroxide and a tertiary amide. It has been found that this problem can be solved by the combined use of a compound and an organic sulfinic acid amide, resulting in high adhesive strength.

The amount of the organic acid, acid anhydride or phosphoric acid ester used in the present invention is 10 parts by weight of the radical-polymerizable monomer.
0.1 to 30 parts by weight or less is suitable. If the amount is more than 30 parts by weight, mechanical performance is deteriorated, which is not preferable.

The organic acid, acid anhydride or phosphoric acid ester may be added to the radical-polymerizable monomer, and an embodiment in which an organic sulfinic acid amide and an organic peroxide are added as a curing agent to the radical-polymerizable monomer. it can.

In the present invention, a tertiary amine may be added as a curing agent component, if desired. That is, the rate of cure is accelerated by adding a tertiary amine in the composition of the present invention. In particular, when t-butylperoxymaleic acid is used as the organic peroxide, it has excellent aesthetics without discoloration even as a quaternary curing agent for organic sulfinamide, organic acid and tertiary amine. Provided is a composition having strong adhesion to tooth and metal. Even when diacyl peroxide is used as the organic peroxide, there is curing in which the discoloration of the cured product is not shown and the curing speed is promoted by appropriately selecting the amount of the tertiary amine used. As the tertiary amine, N, N-dimethyl-p-toluidine, diethanol-
Examples thereof include p-toluidine, N, N-dimethylaminomethacrylate and the like. The amount of the tertiary amine used is 0.01 to 5 parts by weight based on 100 parts by weight of the monomer.

In the present invention, if desired, a photopolymerization initiator and a photopolymerization accelerator may be added. Examples of the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin, benzophenone, 2-chlorothioxanthone, 9,10-anthraquinone, camphorquinone, benzyl, 4,4'-dichlorobenzyl and diacetyl. A so-called ultraviolet sensitizer or visible light sensitizer is exemplified. As the photopolymerization accelerator, N, N-dimethyl-p-toluidine, toluethylamine, trihexylamine, 2-dimethylaminoethanol, N-methyldiethanolamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminomethacrylate Etc. are illustrated.

A plurality of photopolymerization initiators and photopolymerization accelerators may be used, and each is used in an amount of 0.01 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the monomer.

The dental restorative composition of the present invention is used in various applications such as adhesives, cements, composites, floor resins, and veneering crown resins, and may be combined with a filler or a polymer depending on the purpose of use.

Examples of the filler include α-quartz powder, glass beads, silica powder, silicon nitride, alumina silicate, aluminum oxide, barium sulfate, barium glass, strontium glass, colloidal silica, and apatite.
These inorganic fillers are preferably surface-treated in advance with a silane compound or the like in order to enhance binding with the binder resin. As this silane compound. γ
A so-called silane coupling agent such as methacryloxypropyltrimethoxysilane or vinylchlorosilane is used and is coated in an amount of 0.1 to 20 parts by weight with respect to the inorganic filler. It is also useful to use an organic composite filler obtained by kneading and polymerizing these inorganic fillers with a monomer in advance and then pulverizing them.

Examples of the polymer include homopolymers and copolymers of polymethylmethacrylate, polyethylmethacrylate and various polymerizable monomers.

If necessary, a stabilizer is added to the dental restorative material composition of the present invention. As the stabilizer, hydroquinone, hydroquinone monomethyl ether, hydroxymethoxybenzophenone, butylated hydroxytoluene, etc. are preferably used in an amount of 0.01 to 3.0 parts by weight per 100 parts by weight of the monomer.

Hardening agent used in the dental restorative composition of the present invention (a)
The three components of organic sulfinamide, (b) organic peroxide, (c) organic acid, acid anhydride or phosphoric acid ester are in three separate packages or (a) and (b) + (c). It is preferable to store in a package, and it is not preferable to store (a) and (c) in a state where they coexist in the polymerizable monomer. Third if desired
When the amine is added, it is stored in the state of coexisting with (a).
The composition of the present invention exhibits polymerization and curing ability by being stored in 3 or 2 packages and being mixed with each other in use. For example, (1) agent A containing component (a) in the polymerizable monomer and agent B containing component (b) and (c) in the polymerizable monomer are mixed together to prepare a restorative composition To get Or (2) For agent A and filler (b) and
Agent C containing (c) is kneaded together to obtain a restorative composition. Alternatively, (3), agent D and agent B containing the component (a) are kneaded with each other to obtain a restorative composition. Alternatively, (4) a restorative composition is obtained by simultaneously mixing (A), (E), and (F) separately contained in the polymerizable monomer (A), (B), and (C), respectively. Or (5) G containing (b) in the filler
It is used by, for example, kneading the agent with the agent A and the agent F at the same time to obtain a restorative composition, except that the above-mentioned (a) and (c) are not allowed to coexist in the polymerizable monomer. There are no restrictions on other combinations. Further, a liquid agent prepared by dissolving (a) or (b) or (c) or (b) + (c) in a volatile solvent or a monomer solution can be used as a pretreatment agent.

EFFECTS OF THE INVENTION As described above, the dental restorative material composition of the present invention has excellent aesthetics without discoloration over time as compared with the case where the above-described conventional hardener system is used, and further, it has tooth quality, metal and ceramics. It is possible to obtain the property of having a strong adhesive force to the material, which is a great contribution to the field.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Examples Examples 1 to 4 and Comparative Examples 1 to 6 Powder A Silane-treated silica powder 75.0 parts by weight Silane-treated barium sulfate 25.0 parts by weight Liquid B B di (methacryloxyethyl) isophorone diurethane 50.0 parts by weight Ethylene glycol dimethacrylate 35.0 parts by weight 2-Hydroxypropyl methacrylate 15.0 parts by weight Butylated hydroxytoluene 0.05 parts by weight The silane treatment of the filler uses γ-methacryloxypropyltrimethoxysilane against silica or barium sulfate. The usual acetic acid method was used. That is, 100 parts by weight of a solution prepared by dissolving γ-methacryloxypropyltrimethoxysilane in an aqueous 0.1% acetic acid solution to a concentration of 2.0% by weight was mixed with 100 parts by weight of a filler, followed by air drying at 80 ° C. 2 hours at 120 ℃ 30
Surface treatment was performed by heat treatment for minutes.

A curing agent was added to each of the above-mentioned powder A and liquid B as shown in Table 1, and each powder was taken at a powder / liquid ratio of 3.2: 1.0 (weight) and kneaded. Table 2 shows the results of the color tone, the adhesion to metal and the adhesion to bovine tooth enamel.

The adhesion test was carried out by applying the kneaded paste composition to the adherends listed in Table 1, and then applying a stainless rod (SUS-3
(04: 5 mmφ) was pressed, and after hardening the test body, it was immersed in distilled water at 37 ° C. for 24 hours, and then the tensile adhesion strength was measured with a universal tensile tester (manufactured by Toyo Sokki Co., Ltd.) at a tensile speed of 1 mm / min.

As is clear from Tables 1 and 2, Comparative Example 3 using a conventional curing agent system consisting of benzoyl peroxide and a tertiary amine cured in 12 minutes, but the cured product turned yellow and metal-
The adhesion strength between metal and enamel-metal was also extremely low. Comparative Example 4 in which an organic acid is added to the system of Comparative Example 3
The curing time was significantly delayed to 100 minutes, and the adhesive strength was low. Therefore, in Comparative Example 5, the amount of the curing agent was increased in order to obtain an appropriate curing time. In this case, although the metal-metal adhesive strength was improved, the cured product remarkably turned yellow and the enamel-metal. The adhesive strength of was also insufficient. On the other hand, in Comparative Example 6 using a conventional curing agent system consisting of benzoyl peroxide, a tertiary amine and sodium aromatic sulfinate, the cured product did not discolor after a curing time of 5 minutes, but the metal-metal, enamel -Low adhesion strength of the metal.

On the other hand, when the curing agent system of the present invention, that is, the curing agent system comprising organic sulfinic acid amide, organic peroxide and organic acid is used, the cured product is discolored in any case as shown in Examples 1 to 4. , And the metal-metal or enamel-metal adhesive strength showed excellent results. When the organic acid was removed from the curing agent system used in Example 1, the curing time was significantly delayed to 42 minutes as shown in Comparative Example 1, which clearly shows that one component of the curing agent system of the present invention was used. The organic acid used as has the effect of accelerating the polymerization, and when the organic acid is used in combination with the conventional tertiary amine curing agent system of benzoyl peroxide, the polymerization is markedly retarded, which is quite the opposite. It is an effect. Moreover, the use of a radical-polymerizable monomer having an acidic group in one molecule, which is effective as an organic acid for adhesiveness, significantly improved the metal-metal and enamel-metal adhesive strength.

Comparative Example 2 in which the organic peroxide was removed from the curing agent system used in Example 1 did not cure.

From the above results, when the curing agent system of the present invention, that is, the curing agent system composed of organic sulfinamide, organic peroxide and organic acid, is used, compared with the case of using the curing agent system of the prior art, aesthetics It is clear that the adhesiveness, the adhesion to metal, and the adhesion to tooth structure are excellent.

From the comparison between Example 1 and Example 2, the combined use of the tertiary amine with the curing agent system of the present invention is effective in shortening the curing time.

Examples 5 to 7 and Comparative Example 7 Dust C C Silane-treated silica powder 75.0 parts by weight Silane-treated barium sulfate 25.0 parts by weight Liquid D D (methacryloxyethyl) isophorone diurethane 55.0 parts by weight Triethylene glycol di Methacrylate 30.0 parts by weight 2-hydroxylpropyl methacrylate 15.0 parts by weight Butylated hydroxytoluene 0.05 parts by weight The silane treatment of the filler was performed according to the method described in Examples 1 to 4.

A curing agent was added to each of the above-mentioned powder C and liquid D as shown in Table 3, and each powder was mixed at a powder / liquid ratio of 3.2: 1.0 (weight ratio) in the same manner as in Examples 1 to 4. The same tests were performed on the compositions as in Examples 1-4. The results are shown in Table 3.

Examples 8 and 9 E agent Silane-treated silica powder 75.0 parts by weight Silane-treated barium sulfate 25.0 parts by weight t-Butyl peroxide maleic acid 3.0 parts by weight 4-acryloxyethyltrimellitic anhydride 4.5 parts by weight 4 -Acryloxyethyltrimellitic acid 0.5 parts by weight F agent di (methacryloxyethyl) isophorone diurethane 50.0 parts by weight triethylene glycol dimethacrylate 35.0 parts by weight methyl methacrylate 20.0 parts by weight benzenesulfinic acid morpholide 2.0 parts by weight Parts N, N-di (β-hydroxyethyl) -p-toluidine 1.0 parts by weight Butylated hydroxytoluene 0.05 parts by weight G agent Silane-treated silica powder 75.0 parts by weight Silane-treated barium sulfate 25.0 parts by weight t-butyl Peroxymaleic acid 2.0 parts by weight 4-acryloxyethyl trimellitic acid 3.0 parts by weight 4-acryloxy Tyl trimellitic anhydride 2.0 parts by weight H agent di (methacryloxyethyl) trimethyl hexamethylene diurethane 55.0 parts by weight triethylene glycol dimethacrylate 30.0 parts by weight 2-hydroxypropyl methacrylate 15.0 parts by weight N, N-dimethyl-p-toluene sulfinic acid amide 1.0 part by weight N, N-di (β-hydroxyethyl) -p-toluidine 0.5 part by weight Butylated hydroxytoluene 0.05 part by weight In addition, the silane treatment was performed in Examples 1 to 4. It carried out on the same conditions as the acetic acid method. Adhesion of a composition prepared by mixing the above E agent and F in a weight ratio of 3.5: 1 and a composition prepared by similarly mixing the agent G and H agent in a weight ratio of 3.5: 1 to various adherends. The results of the sex test are shown in Table 4 as Examples 8 and 9. The adhesion test was performed according to Examples 1 to 4.

As is clear from Table 4, the composition of the present invention strongly adheres to the sandblasted metal at 446 Kgf / cm ² and 496 Kgf / cm ^2, and is not treated not only on the tooth enamel but also on the dentin. In the state, it was found to have excellent adhesiveness of 45 Kgf / cm ² and 46 Kgf / cm ² . Furthermore, when a dental 130 kgf / cm ² in porcelain, 120 kgf / cm ² and high adhesion revealed.

Examples 10 to 11 Agent I parts by weight Polymethylmethacrylate powder 85.0 Polyethylmethacrylate powder 15.0 t-Butylperoxymaleic 3.0 Acid 4-acryloxyethyltrimellitic acid 5.0 Agent J parts by weight Silane-treated silica powder 60 .0 polymethylmethacrylate powder 35.0 polyethylmethacrylate powder 5.0 t-butylperoxymaleic 3.0 acid 4-acryloxyethyltrimellitic acid 5.0 anhydride K agent parts by weight methylmethacrylate 75.0 ethylmethacrylate 20.0 2, 2-bis (methacryloxyethoxy) 5.0 phenyl) propane p-toluenesulfinic acid morpholide 2.0 butylated hydroxytoluene 0.05 L agent parts by weight methyl methacrylate 95.0 2,2-bis (methacryloxyethoxy 5.0 phenyl) propane p-toluene Sulfinic acid morpholide 2.0 Butyl Hydroxytoluene 0.05 Curing time of the composition prepared by mixing the above-mentioned agents I and K and agents J and L in the powder-liquid ratio shown in Table 5, the color tone of the cured product, and the adhesion to various adherends. Tested for sex. The results are shown in Table 5.

The adhesion test method and the silica silane treatment method are described in Examples 1 to 1.
It carried out according to 4.

Example 12 Pretreatment Part by Weight Methyl Methacrylate 88 4-Acryloxyethyltrimellitic Acid 10 Anhydride t-Butyl Peroxymaleic Acid 2 The above pretreatment agent was further applied to the bovine dentin and the adhered surface of the metal. Then, using the composition described in Example 8, an adhesion test of dentin and a metal (Ni-Cr alloy: manufactured by Shofu Co., Ltd.) was performed, and an adhesion strength of 70 Kgf / cm ² was obtained.

Example 13 Using a Matsukaze Superlux Daylight (manufactured by Matsukaze Co., Ltd.) according to the instruction for use, a dye leakage test was carried out. 40 parts by weight of di (methacryloxyethyl) trimethylhexamethylenediurethane and bisphenol were used. A Diglycidyl methacrylate 10 parts by weight, triethylene glycol dimethacrylate 30 parts by weight, neopentyl glycol dimethacrylate 10 parts by weight, 2-hydroxyethyl methacrylate 10 parts by weight, butylated hydroxytoluene 0.1 parts by weight A monomer mixture for 2 minutes And then t-
Butyl peroxymaleic acid 3.0 parts by weight, 4-acryloxyethyl trimellitic acid 1.5 parts by weight, N, N on the other hand
-Dimethyl-benzenesulfinamide 2.0 parts by weight,
A two-part composition containing 1 part by weight of benzyl and 2.0 parts by weight of N-methyldiethanolamine was prepared, and the above test was conducted.

After forming a cavity with a diameter of 3 mm and a depth of 2 mm on a human freshly extracted tooth,
After phosphoric acid etching treatment, washing with water and drying, applying an equal volume mixture of the above two solutions, blowing air, and filling with Matsukaze Super Lux Daylight, Matsukaze Grip Light (made by Shofu Co., Ltd. A dye leakage test was conducted on a photopolymerized product irradiated with a light beam irradiator for 30 seconds, and as a result, almost no dye penetration was observed in the cavity wall and cavity. On the other hand, when a dye leakage test was carried out in the same manner as above using a liquid agent in which all the hardener components other than benzyl and N-methyldiethanolamine were removed from the hardener system having the above-mentioned two-component constitution, the dye invasion caused the cavity wall. After that, it was recognized up to the pulp cavity.

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Claims (11)

[Claims] 1. A dental restorative material composition comprising a radically polymerizable monomer and a curing agent, wherein the curing agent is (a) organic sulfinic acid amide (b) organic peroxide (c) organic acid, acid anhydride Alternatively, a dental restorative composition comprising a phosphoric acid ester. 2. The dental restorative material composition according to claim 1, wherein the organic sulfinic acid amide is an aromatic sulfinic acid amide. 3. The aromatic sulfinic acid amide is benzenesulfinic acid morpholide, p-toluenesulfinic acid morpholide, N, N-dimethyl-p-toluenesulfinic acid amide, N, N-dimethyl-benzenesulfinic acid amide and the like. The dental restorative material composition according to claim 2. 4. The organic peroxide is t-butyl peroxymaleic acid, benzoyl peroxide and 4,4 '.
-The dental restorative composition according to claim 1, which is dichlorobenzoyl peroxide. 5. An organic acid, an acid anhydride or a phosphoric acid ester has at least one carboxyl group, acid anhydride group or phosphoric acid ester group in one molecule, and is capable of at least one radical polymerization. The dental restorative composition according to claim 1, which has a structure having an unsaturated group. 6. The dental restorative composition according to claim 1, wherein the organic acid is 4-acryloxyethyl trimellitic acid or 4-methacryloxyethyl trimellitic acid. 7. The dental restorative composition according to claim 1, wherein the acid anhydride is 4-acryloxyethyl trimellitic anhydride or 4-methacryloxyethyl trimellitic anhydride. 8. The dental restorative composition according to claim 1, wherein the phosphoric acid esters are bis (2-methacryloxyethyl) phosphoric acid and [(2-methacryloxyethyl) phenyl] phosphoric acid. . 9. The curing agent is (a) 0.01 to 20 parts by weight of organic sulfinamide (b) 0.01 to 10 parts by weight of organic peroxide (100 parts by weight) with respect to 100 parts by weight of a radical-polymerizable monomer. ) The dental restorative material composition according to claim 1, comprising 0.1 to 30 parts by weight of an organic acid, an acid anhydride or a phosphoric acid ester. 10. The dental restorative composition according to claim 1, further comprising fillers or polymer particles. 11. The dental restorative material composition according to claim 1, further comprising a volatile solvent.