JP2008088086A - Dental composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental composition having high storage stability and excellent adhesiveness to the dentin, which is composed of one of a monomer, an oligomer and a prepolymer of a (meth)acrylate and is polymerizable and hardenable through a redox reaction of a peroxide, wherein at least one of a monomers, an oligomers and a prepolymer of the (meth)acrylate has an acid group. <P>SOLUTION: The dental composition is composed of a first component containing at least one of the monomers, oligomers or prepolymers of a (meth)acrylate having an acid group and a second component containing at least one of monomers, oligomers or prepolymers of a (meth)acrylate free of an acid group, wherein a hydrogen peroxide polyvinyl pyrrolidone complex is added as a polymerization initiator to one component and a salt of an ascorbic acid derivative and/or a thiourea derivative is added as a reducing agent for the polymerization initiator to the other component. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dental composition that has good adhesion to a tooth and exhibits good storage stability for a long period of time in a storage state before polymerization of a polymerizable resin.

  Fillers and adhesives using polymerizable resins such as methacrylate used for dentistry are composed of one component and used for photopolymerization, and two components are mixed and mixed. Some are kneaded and used. In a product composed of two components, two or more kinds of polymerization catalysts are separately blended and mixed at the time of use to polymerize a polymerizable resin and used.

  As a two-component product, the first paste comprises a polymerizable methacrylate monomer system comprising a cross-linking methacrylate monomer, at least one comonomer methacrylate diluent and a free radical generating catalyst, and an inorganic filler. The paste of 2 is a curable dental restorative material comprising a polymerizable methacrylate monomer system comprising a cross-linking methacrylate monomer, at least one comonomer methacrylate diluent and a tertiary aromatic amine polymerization accelerator, and an inorganic filler. (For example, refer to Patent Document 1), a dental curable composition containing a polymerizable monomer, an inorganic filler, and a chemical polymerization initiator composed of a tertiary amine and an organic peroxide. Divided into two pastes, a first paste containing a secondary amine and a second paste containing an organic peroxide. Dental curable composition are (e.g., see Patent Document 2.) Have been proposed.

Thus, in the case of a so-called redox polymerization product consisting of two components and polymerizing a polymerizable resin blended in at least one component, the peroxide and the reducing substance are blended separately in the two components. The As peroxides for redox polymerization, Patent Document 1 discloses benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, and Patent Document 2 discloses t-butyl hydroperoxide, cumene hydroperoxide, peroxide. Examples include dibutyl, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, and benzoyl peroxide.
Further, as the reducing substance, N, N-dimethyl-P-toluidine and N, N-dihydroxyethylene-P-toluidine tertiary aromatic amines are used in Patent Document 1 and aromatic tertiary materials are used in Patent Document 2. Examples are amines and aliphatic tertiary amines.

  Such peroxides represented by benzoyl peroxide for redox polymerization cause decomposition and radical generation during storage at room temperature, which may cause polymerization of polymerizable resins coexisting in the components, or peroxides. There was a problem that the product itself was deactivated and the polymerization and curing reactivity decreased with time. Even when a peroxide is blended in a component mainly composed of an aqueous solution without blending a polymerizable resin on the component side where the peroxide is blended, the peroxide is decomposed and deactivated during storage. As a result, there is a problem that the curing reactivity is lowered. Usually, the peroxide is most stable when stored in a sealed container in a dry state, but it has been difficult to exist in a stable state together with the polymerizable resin or in an aqueous solution for a long period of time.

  In addition, the rate of peroxide decomposition and radical generation depends on the temperature, and because of the slow decomposition and radical generation rate at low temperatures, many conventional products are recommended to be refrigerated. Refrigerated storage is also costly during transportation, and the user is troublesome to take it out of the refrigerator when in use. Even if the product is not recommended for refrigerated storage, long-term storage stability is not maintained at room temperature, causing discoloration, gelation of the paste, or a decrease in curing reactivity.

Japanese Patent Publication No. 6-2651 Japanese Patent Laid-Open No. 2005-170813

  Accordingly, the present invention provides a (meth) acrylate comprising at least one of a (meth) acrylate monomer, oligomer, and prepolymer as a polymerizable resin that is polymerized and cured using a redox reaction of peroxide. It is an object of the present invention to provide a dental composition using at least one of the above monomers, oligomers and prepolymers as a dental composition having high storage stability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the hydrogen peroxide polyvinyl pyrrolidone complex has hydrogen peroxide bonded to the polymer chain, and in a paste containing water, acid or polymerizable resin. Focusing on the fact that hydrogen peroxide is difficult to release, if a salt and / or thiourea derivative of an ascorbic acid derivative is used as a reducing substance that decomposes this hydrogen peroxide polyvinylpyrrolidone complex and generates a radical, If the hydrogen peroxide polyvinylpyrrolidone complex and the salt and / or thiourea derivative of the ascorbic acid derivative are not allowed to coexist, sufficient storage is possible for a long period of time even at room temperature. If the hydrogen peroxide polyvinylpyrrolidone complex and the salt and / or thiourea derivative of the ascorbic acid derivative coexist, the polymer is rapidly polymerized. It the present invention has been completed to investigate that can be a dental composition capable.

  That is, the present invention is a polymerization comprising at least one of (meth) acrylate monomers, oligomers and prepolymers comprising at least one of (meth) acrylate monomers, oligomers and prepolymers. A hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator for polymerizing and curing the polymerizable resin, and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of the polymerization initiator It is a dental composition characterized by containing.

The dental composition includes at least one of (meth) acrylate monomers, oligomers and prepolymers having an acid group, and a first component containing a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator,
A second containing at least one of (meth) acrylate monomer, oligomer and prepolymer having no acid group, and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of a polymerization initiator in the first component An embodiment comprising the components (hereinafter referred to as the first embodiment),
At least one of (meth) acrylate monomer, oligomer and prepolymer having an acid group, and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of a polymerization initiator in the second component described later A first component;
An embodiment (hereinafter referred to as a second embodiment) comprising at least one of a (meth) acrylate monomer having no acid group, an oligomer and a prepolymer, and a second component containing a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator It is preferable that
In these embodiments, the salt of the ascorbic acid derivative as the reducing substance of the polymerization initiator is easily decomposed in the presence of water or an acid. Therefore, when water is included in the component containing the reducing substance of the polymerization initiator, polymerization is performed. When the reducing substance of the initiator is a thiourea derivative, it is preferable to include water.

  In these embodiments, the second component containing at least one of (meth) acrylate monomer, oligomer and prepolymer having no acid group includes a filler that reacts with the acid group, or has an acid group (meta ) In the case where the first component containing at least one of acrylate monomer, oligomer and prepolymer further contains at least one of (meth) acrylate monomer, oligomer and prepolymer having no acid group, One or both of the second components may further contain a filler that does not react with the acid, and one or both of the first component and the second component may contain a thickener.

  The dental composition according to the present invention comprises at least one of (meth) acrylate monomer, oligomer and prepolymer, and has at least one of (meth) acrylate monomer, oligomer and prepolymer having an acid group therein. A polymerizable resin containing and a dental composition for polymerizing and curing the polymerizable resin using a redox reaction of a peroxide, and a polymer chain as a polymerization initiator for polymerizing and curing the polymerizable resin Hydrogen peroxide polyvinyl pyrrolidone complex with the property that it is difficult to release hydrogen peroxide in components including water, acid and polymerizable resin is used. As a reducing substance, ascorbic acid derivative salt and / or thiourea derivative is used, it has excellent storage stability and good adhesion to tooth It is a family composition.

The present invention comprises at least one of (meth) acrylate monomers, oligomers and prepolymers, and it contains at least one of (meth) acrylate monomers, oligomers and prepolymers having acid groups. Resin, a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator for polymerizing and curing the polymerizable resin, and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of the polymerization initiator. A dental composition characterized by
A first component comprising at least one of (meth) acrylate monomers, oligomers and prepolymers having an acid group, and a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator;
A second containing at least one of (meth) acrylate monomer, oligomer and prepolymer having no acid group, and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of a polymerization initiator in the first component A first embodiment comprising the components,
At least one of (meth) acrylate monomer, oligomer and prepolymer having an acid group, and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of a polymerization initiator in the second component described later A first component;
It is preferable to be a second embodiment comprising at least one of a (meth) acrylate monomer having no acid group, an oligomer and a prepolymer, and a second component containing a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator. .

  The hydrogen peroxide polyvinyl pyrrolidone complex used as a polymerization initiator in the present invention is a substance containing hydrogen peroxide in polyvinyl pyrrolidone, for example, a powdery complex as described in JP-A-6-505765. Is the body. The concentration of hydrogen peroxide in the complex is preferably 1 to 30% by weight. This hydrogen peroxide polyvinylpyrrolidone complex keeps hydrogen peroxide in a stable state for a long time even in harsh environments such as aqueous solutions and acids, and at the same time, polyvinylpyrrolidone itself is not affected by hydrogen peroxide for a long time. There are features. The blending amount of the hydrogen peroxide polyvinyl pyrrolidone complex in the dental composition is preferably 0.01 to 15% by weight. If it is less than 0.01% by weight, the effect as a polymerization initiator is low, and even if it exceeds 15% by weight, it is difficult to improve the effect of polymerization.

  In order to decompose hydrogen peroxide from such a stable hydrogen peroxide polyvinylpyrrolidone complex to generate radicals and act as a polymerization initiator, a salt of ascorbic acid derivative and / or a thiourea derivative is required as a reducing substance. And Examples of the salt of the ascorbic acid derivative include sodium ascorbate, calcium ascorbate, and potassium ascorbate. Examples of thiourea derivatives include 1-acetyl-2-thiourea, 1-phenyl-2-thiourea, trimethylthiourea, N-methylthiourea, 1-allyl-3- (2-hydroxyethyl) -2- Examples thereof include thiourea and 1- (2-tetrahydrofurfuryl) -2-thiourea, and 1-acetyl-2-thiourea is particularly preferable.

  In the dental composition according to the present invention using such a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance, it is polymerized. The polymerizable resin consists of at least one of (meth) acrylate monomers, oligomers and prepolymers, and has (meth) acrylate monomers and oligomers with acid groups to improve adhesion to the tooth. , A polymerizable resin containing at least one prepolymer is used.

  Such a polymerizable resin comprises a hydrogen peroxide polyvinyl pyrrolidone complex as a polymerization initiator coexisting with a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance. Since the polymerization is initiated when hydrogen peroxide is decomposed to generate radicals and the action as a polymerization initiator occurs, at least the hydrogen peroxide polyvinyl pyrrolidone complex as a polymerization initiator and a reducing substance before the polymerization starts It is necessary that the salt of the ascorbic acid derivative and / or the thiourea derivative does not coexist.

  As described above, in order to make the hydrogen peroxide polyvinylpyrrolidone complex as the polymerization initiator and the salt and / or thiourea derivative as the reducing substance coexist before the polymerization is started, the dental composition A first component containing at least one of (meth) acrylate monomer, oligomer and prepolymer having an acid group, and a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator, and a (meth) acrylate having no acid group A first aspect comprising at least one of a monomer, an oligomer and a prepolymer, and a second component containing a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of a polymerization initiator in the first component Or at least one of (meth) acrylate monomers, oligomers and prepolymers with acid groups A first component containing a salt of an ascorbic acid derivative and / or a thiourea derivative as a reducing substance of a polymerization initiator in the second component described later, and a (meth) acrylate monomer, oligomer and prepolymer having no acid group And a second component comprising a hydrogen peroxide polyvinyl pyrrolidone complex as a polymerization initiator and having a good storage stability with good adhesion to the tooth. Since it can have excellent curability, it is preferable.

  The hydrogen peroxide polyvinyl pyrrolidone complex as a polymerization initiator is more stable at a pH of about 2.5 when blended in a composition containing water, so that the dental composition is composed of two components. Is preferably blended with the hydrogen peroxide polyvinylpyrrolidone complex in the first component containing at least one of (meth) acrylate monomer, oligomer and prepolymer having an acid group as in the first embodiment, The blending amount of the hydrogen peroxide polyvinyl pyrrolidone complex as the polymerization initiator in the first component is preferably 0.01 to 15% by weight. This is because if it is less than 0.01% by weight, it is difficult to obtain sufficient polymerization after mixing the two components, and if it exceeds 15% by weight, it is difficult to improve the polymerization effect.

  (Meth) acrylate monomers, oligomers and prepolymers having acid groups are polymerized and cured by themselves to form a matrix of a dental composition, but (meth) acrylate monomers, oligomers and prepolymers having no acid groups. When a polymer is also present, it is polymerized and cured together with the (meth) acrylate monomer, oligomer and prepolymer having no acid group to form a matrix of a dental composition. The amount of the (meth) acrylate monomer / oligomer / prepolymer having an acid group is preferably 3 to 80% by weight, preferably less than 3% by weight, based on the first component. Even if it exceeds wt%, the adhesiveness tends to decrease.

  The (meth) acrylate monomer, oligomer or prepolymer having an acid group is preferably a (meth) acrylate monomer having a phosphate group or a carboxyl group, and one or more phosphate groups in one molecule. Polymeric monomers, oligomers, and prepolymers that have a phosphoric acid group that is more acidic than carboxyl groups, so it is highly effective in dissolving the smear layer on the tooth surface and demineralizing the tooth, especially for enamel Demonstrate the effect of improving high adhesion.

  Examples of the polymerizable monomer having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen. Phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl phenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 1,3-di (meth) acryloyl Propane-2-dihydrogen phosphate, 1,3-di (meth) acryloylpropane-2-phenylhydrogen phosphate, bis [5- {2- (meth) acryloyloxyethoxy carbonate Boniru} heptyl] hydrogen phosphate, and the like. Among them, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate is particularly preferable from the viewpoints of adhesion and stability of the monomer itself. These polymerizable monomers having a phosphoric acid group may be used alone or in admixture of two or more.

  Examples of the monomer having a carboxyl group include 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, 4- (meth) acryloxydecyl trimellitic acid, 4- (meta ) Acryloxydecyl trimellitic anhydride, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di (meth) acryloyloxypyromellitic acid, 2- (meth) acryloyloxyethylmaleic acid 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and the like. Among these, 4- (meth) acryloxyethyl trimellitic acid and 4- (meth) acryloxyethyl trimellitic anhydride are particularly preferable from the viewpoint of adhesiveness.

In order to enhance the action of the reducing substance in an anionic state, for subsequent electron transfer and for the stability of the hydrogen peroxide polyvinylpyrrolidone complex as the polymerization initiator, the polymerization initiator of the dental composition It is preferable that 1 to 30% by weight of water is blended in the component containing the first component (the first component in the first embodiment and the second component in the second embodiment). If the blending is less than 1% by weight or more than 30% by weight, it is difficult to obtain the above effect.
Also, water may be added to the component containing the reducing substance of the polymerization initiator (the second component in the first aspect, the first component in the second aspect), but with the reducing substance of the polymerization initiator, A salt of an ascorbic acid derivative is easily decomposed in the presence of water and an acid. Therefore, when water is added to a component containing a reducing substance of a polymerization initiator, the reducing substance of the polymerization initiator is a thiourea derivative. It is preferable.

  The first component of the two-component dental composition (first embodiment and second embodiment) is blended with at least one of (meth) acrylate monomer, oligomer and prepolymer having no acid group. Also good. As this component, monomers, oligomers and prepolymers conventionally used can be used without particular limitation. For example, a monomer or resin having an unsaturated double bond such as unsaturated polyester is generally used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, Noxyethyl (meth) acrylate, 2,2-bis (meth) acryloxyphenylpropane, 2,2-bis [4- (2-hydroxy-3- (meth) acryloxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) ac Rate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and urethane in the molecule There are (meth) acrylates having a bond, especially di-2- (meth) acryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate. These methacrylates and acrylates can be used alone or in admixture of two or more, and can also be used as oligomers and prepolymers.

  When the (meth) acrylate monomer, oligomer or prepolymer having no acid group is blended in the first component, the blending amount in the first component is preferably 5 to 80% by weight. If it is less than 5% by weight, the strength of the dental composition tends to decrease, and if it exceeds 80% by weight, the adhesion to the tooth tends to decrease.

  In the second component of the dental composition comprising the two components (first and second embodiments), at least one of (meth) acrylate monomer, oligomer and prepolymer having no acid group is blended. The (meth) acrylate monomer, oligomer and prepolymer having no acid group are polymerized and cured together with all the (meth) acrylate monomer, oligomer and prepolymer in the first component to form a matrix of the dental composition. As the (meth) acrylate monomer, oligomer and prepolymer having no acid group in the second component, the same type of materials as those in the first component can be used.

  The salt and / or thiourea derivative of the ascorbic acid derivative as the reducing substance blended in the first component in the second aspect in the second component in the first aspect is mixed with the other component to form an anion. Thus, there is an effect of generating radicals by decomposing hydrogen peroxide of the hydrogen peroxide polyvinylpyrrolidone complex which is a polymerization initiator in the other component. Examples of the salt of the ascorbic acid derivative include sodium ascorbate, calcium ascorbate, and potassium ascorbate. Although the salt of this ascorbic acid derivative is easily decomposed in the presence of water or an acid, the thiourea derivative is stable even in the presence of water or an acid. Examples of the thiourea derivative include -acetyl-2-thiourea, 1- Phenyl-2-thiourea, trimethylthiourea, N-methylthiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, 1- (2-tetrahydrofurfuryl) -2-thiourea, etc. 1-acetyl-2-thiourea is particularly preferable.

  In addition, you may mix | blend an amine compound (Aromatic tertiary amine, aliphatic tertiary amine) as a polymerization adjuvant of the hydrogen peroxide polyvinylpyrrolidone complex which is a polymerization initiator. Specifically, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-diethylaminoethyl methacrylate, triethanolamine, methyl 4-dimethylbenzoate, ethyl 4-dimethylbenzoate, isoamyl 4-dimethylaminobenzoate, triethylamine, N-ethyldiethanolamine and the like. Of course, these may be used singly or in combination of two or more, but it is necessary that they are not coexisting with the hydrogen peroxide polyvinylpyrrolidone complex which is a polymerization initiator. This amine compound reacts with radicals released upon reaction of hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of the polymerization initiator. And has the effect of promoting polymerization.

  In the dental composition comprising the two components according to the present invention (first and second embodiments), one or both of the first component and the second component may further contain a filler that does not react with acid. preferable. In the case of the first component, the filler that does not react with the acid needs to be stable to (meth) acrylate monomers, oligomers, and prepolymers having an acid group, and improves the mechanical strength of the dental composition. effective. The blending amount of the filler that does not react with the acid with respect to the first component or the second component is preferably 1 to 85% by weight, and if it is less than 1% by weight, the effect of increasing the strength of the dental composition tends to be low, 85 When the blending amount exceeds 5% by weight, the adhesion to the tooth tends to be lowered.

  As a filler that does not react with an acid, silica such as colloidal silica produced by spray pyrolysis of a silane compound or the like is generally used. In addition, alumina, zinc white, zirconia, magnesia, titania, glass, etc. An inorganic filler such as is preferable. Further, a filler obtained by pulverizing a polymer of the (meth) acrylate monomer, oligomer, or prepolymer can also be used.

  The average particle diameter of the filler that does not react with the acid and the filler that reacts with the acid that may be incorporated in the second component described later is preferably 0.05 to 20 μm, and the average particle diameter is less than 0.05 μm. When the fine powder is used, the operability of the dental composition is liable to deteriorate, and when it exceeds 20 μm, the dental composition according to the present invention is used for adhesion between the tooth and the dental prosthesis. There is a tendency that the gap between the dental prosthesis and the teeth becomes too large, and the fitting accuracy of the dental prosthesis is deteriorated. Furthermore, in the case of inorganic fillers, those subjected to silane treatment by a usual method can also be used.

  In the dental composition according to the present invention consisting of two components (first and second embodiments), when water is contained in the first component and / or the second component, the second component further contains an acid. It preferably contains a reactive filler. The filler that reacts with the acid is a fluoroaluminosilicate glass powder that can be cured by causing a cement reaction (acid-base reaction) in the presence of a (meth) acrylate monomer having an acid group in the first component and water, Metal oxide powders used in dental zinc phosphate cement powder and dental carboxylate cement powder are preferred.

The fluoroaluminosilicate glass powder is a glass powder conventionally used for dental glass ionomer cement, and contains Al ³⁺ , Si ⁴⁺ , F ⁻ , O ²⁻ as main components, and Sr ^2+. And / or a fluoroaluminosilicate glass powder containing Ca ²⁺ . Further, Al ³⁺ : 10 to 21% by weight, Si ⁴⁺ : 9 to 24% by weight, F ⁻ : 1 to 20% by weight, and a total of 10 to 34 of Sr ²⁺ and Ca ²⁺ with respect to the total weight of the glass. It is preferable that it is weight%. The ratio of these main components greatly affects operability and physical properties such as curing speed, final strength, and solubility. When the ratio of Al ³⁺ is less than 10% by weight, curing tends to be slow and strength tends to be low. When the proportion of Al ³⁺ exceeds 21% by weight, it is difficult to produce glass, and transparency tends to be lowered and aesthetics tend to be inferior. When the proportion of Si ⁴⁺ is less than 9% by weight, it is difficult to produce glass. When the proportion of Si ⁴⁺ exceeds 24% by weight, the curing rate tends to be slow, and the strength tends to be low, which tends to cause a problem in durability. When the proportion of F ⁻ is less than 1% by weight, it tends to be difficult to produce glass. When the proportion of F ⁻ exceeds 20% by weight, the reactivity tends to decrease. When the total of Sr ²⁺ and Ca ²⁺ is less than 10% by weight, the reactivity tends to be low, and in this case, it tends to be difficult to produce glass. When the total of Sr ²⁺ and Ca ²⁺ exceeds 34% by weight, the reaction tends to be too fast and it becomes difficult to actually use. Such a fluoroaluminosilicate glass can be produced by a known glass production method.

  Further, the metal compound powder used in dental zinc phosphate cement powder and dental carboxylate cement is a metal oxide powder mainly composed of zinc oxide, and these are generally 70 to 90 wt. % Is mixed with 10 to 30% by weight of a metal oxide such as magnesium oxide, sintered at a high temperature of 700 ° C. or higher, cooled, and pulverized with a ball mill or the like to produce a powder. Examples of other metal oxides include metal oxides such as strontium oxide, silicon dioxide, ferric oxide, and yttrium oxide.

  A thickener may be included in one or both of the first component and the second component. As this thickener, a thickener conventionally used in dentistry can be used, and fumed silica is particularly preferable.

  Of course, a photopolymerization catalyst, an antibacterial agent, a pigment and the like that are usually used can be appropriately blended in the dental cement according to the present invention as needed.

Hereinafter, the present invention will be specifically described with reference to examples.
"Preparation of first and second ingredients"
Table 1 shows the composition of the first component and the second component used in each Example and Comparative Example.

Abbreviations in Table 1 are as follows.
MDP: 10-methacryloyloxydecyl dihydrogen phosphate
PM2: Bismethacryloxyethyl phosphate
4META: 4-Methacryloxyethyl trimellitic anhydride

TEGDMA: Triethylene glycol dimethacrylate
GDMA: 2-hydroxy-1,3-dimethacryloxypropane
HEMA: Hydroxyethyl methacrylate

PAA: Polyacrylic acid (average molecular weight 15,000)
SiO2 filler: silicon dioxide
P amine: N, N-bis (2-hydroxyethyl) -p-toluidine

K30: Hydrogen peroxide polyvinylpyrrolidone complex (manufactured by ISP, trade name: Peroxydone K-30) XL-10: Hydrogen peroxide polyvinylpyrrolidone complex (manufactured by ISP, trade name: Peroxydone XL-10)

DW: Distilled water glass powder I: Fluoroaluminosilicate glass powder I
Glass powder II: Fluoroaluminosilicate glass powder II
Metal oxide powder: Metal oxide powder mainly composed of zinc oxide

BPO: Benzoyl peroxide
BSNa: Sodium benzenesulfinate dihydrate
CQ: Camphorquinone

IA acid Na: sodium isoascorbate monohydrate
LA acid Ca: calcium L-ascorbate dihydrate
NATU: 1-acetyl-2-thiourea
TMTU: Trimethylthiourea
IA: 6-tert-butyl-2,4-xylenol
EPA: ethyl 4-dimethylaminobenzoate

“Preparation of powdered fluoroaluminosilicate glass powder”
Table 2 shows the composition of fluoroaluminosilicate glass powders I and II (shown as glass powder I and glass powder II in Table 1).

  The raw materials were sufficiently mixed and held in a high-temperature electric furnace at 1200 ° C. for 5 hours to melt the glass. After melting, the mixture is cooled, ground for 10 hours using a ball mill, and 1 g of γ-methacryloxypropyltrimethoxysilane is added with 9 g of ethanol to 100 g of powder after passing through a 200 mesh (ASTM) sieve. The silane coupling treatment was performed to obtain fluoroaluminosilicate glass powder.

"Preparation of powdered metal oxide powder"
Table 3 shows the composition of metal oxide powder used in dental zinc phosphate cement powder and dental carboxylate cement powder.

  The raw materials were sufficiently mixed and held in a high temperature electric furnace at 1000 ° C. for 5 hours for sintering. It cooled after sintering, and it grind | pulverized for 10 hours using the ball mill, and let it pass through a 200 mesh (ASTM) sieve, and was set as the metal oxide powder which has a zinc oxide as a main component.

"Preservation test"
After the samples of each Example and Comparative Example were stored at room temperature (about 23 ° C.) for 1 year or in a thermostatic chamber (about 45 ° C.) for 1 month, the first component 1.0 g and the second component 1.0 g Was measured on a kneaded paper and mixed uniformly by performing a kneading operation for 40 seconds using a spatula. Table 4 shows a comparison with the curing time before the storage test of this sample.

  As can be seen from Table 4, Examples 1 to 10, which are dental compositions according to the present invention, are dental compositions having excellent storage stability with no deterioration of the polymerization catalyst and almost no change in curing time. .

Claims (11)

  A polymerizable resin comprising at least one of (meth) acrylate monomers, oligomers and prepolymers, and containing at least one of (meth) acrylate monomers, oligomers and prepolymers having an acid group therein; A hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator for polymerizing and curing the polymerizable resin, and a salt and / or thiourea derivative of an ascorbic acid derivative as a reducing substance of the polymerization initiator. A dental composition characterized. At least one of (meth) acrylate monomers, oligomers and prepolymers with acid groups;
A first component comprising a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator;
At least one of (meth) acrylate monomers, oligomers and prepolymers without acid groups;
The dental composition according to claim 1, comprising a second component containing a salt of an ascorbic acid derivative and / or a thiourea derivative as a reducing substance of the polymerization initiator in the first component.   The dental composition according to claim 2, comprising water in the first component.   The dental composition according to claim 2 or 3, wherein the reducing substance in the second component is a thiourea derivative, and water is contained in the second component. At least one of (meth) acrylate monomers, oligomers and prepolymers with acid groups;
A first component comprising a salt of an ascorbic acid derivative and / or a thiourea derivative as a reducing substance of a polymerization initiator in a second component described later;
At least one of (meth) acrylate monomers, oligomers and prepolymers without acid groups;
The dental composition according to claim 1, comprising a second component containing a hydrogen peroxide polyvinylpyrrolidone complex as a polymerization initiator.   The dental composition according to claim 5, comprising water in the second component.   The dental composition according to claim 5 or 6, wherein the reducing substance in the first component is a thiourea derivative, and water is contained in the first component.   The dental composition according to any one of claims 2 to 7, wherein the second component contains a filler that reacts with an acid.   The dental composition according to any one of claims 2 to 8, wherein the first component further comprises at least one of a monomer, an oligomer and a prepolymer of (meth) acrylate having no acid group.   The dental composition according to any one of claims 2 to 9, further comprising a filler that does not react with an acid, in one or both of the first component and the second component.   The dental composition according to any one of claims 2 to 10, comprising a thickener in one or both of the first component and the second component.