JP5271764B2 - Dental filling kit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental packing kit composed of a dental adhesive and a dental composite resin that can provide sufficient adhesive strength even to dentine of the cavity bottom and cavity wall to which visible light does not fully reach when the dental adhesive and the dental composite resin are polymerized and cured by one-step irradiation of light. <P>SOLUTION: The dental packing kit includes the dental adhesive (A) containing an polymerizable monomer (a) containing an acidic group, water (b) and an amine based reducer (c), and the dental composite resin (B) containing a polymerizable monomer (d) not containing an acidic group, an inorganic peroxide (e), a photopolymerization initiator (f) and a filler (g). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a dental filling kit. More particularly, the present invention relates to a dental filling kit including a dental adhesive and a dental composite resin.

  One of the methods for repairing dental materials damaged by caries or the like (which is a general term for enamel, dentin, and cementum) is a filling restoration using a filling composite resin. Since the composite resin used for this restoration is usually not adhesive to the tooth, various adhesive methods using adhesives are used when filling the cavity with the cavity after removing the caries. ing. Conventionally, after pretreatment (etching treatment) using an acid etching agent such as phosphoric acid aqueous solution on the surface of the tooth, a bonding agent, which is an adhesive, is applied to bond the tooth and the composite resin. In general, a so-called acid etching type adhesion method has been used. However, in recent years, a self-etching primer containing an acidic group-containing polymerizable monomer and a hydrophilic polymerizable monomer is applied to the surface of the tooth without using an acid etchant, and then washed with water. In addition, a so-called self-etching type bonding method in which a bonding agent is applied is widely used. Recently, a one-step dental adhesive that combines the functions of a self-etching primer and a bonding agent has been put into practical use. Here, in order for the dental adhesive to exhibit sufficient adhesion to the dentin, particularly dentin, the demineralization action that dissolves the dentin surface with an acidic component, the polymerizable monomer component is the dentin It is necessary to have an osmotic effect that penetrates into collagen and a curable effect that the penetrated polymerizable monomer component hardens to form a hybrid layer with collagen.

  Filling composite resins are roughly classified into chemical polymerization type and photopolymerization type due to the difference in polymerization mode. As a chemical polymerization type composite resin, a combination of an organic peroxide (oxidizing agent) such as benzoyl peroxide and a redox polymerization initiator using a reducing agent such as amine has been put into practical use. The chemical polymerization type composite resin containing this redox polymerization initiator is a two-paste type that is divided and stored in a paste containing an oxidizing agent and a paste containing a reducing agent, and both pastes are mixed immediately before use. There are many. On the other hand, as the photopolymerizable composite resin, a one-paste type compound in which a photopolymerization initiator having an absorption wavelength in the visible light region is generally used. This photopolymerizable composite resin has been widely used in clinical use in recent years because it is simpler to operate than a chemical polymerization type composite resin.

  In restoration using a photopolymerizable composite resin, generally, first, an adhesive is applied to the surface of the cavity and the adhesive is cured by irradiation with visible light, and then the cavity is filled with the composite resin and visible light is again emitted. A two-stage photopolymerization method in which the composite resin is cured by irradiation is used. As described above, in the case of a general repair method, it is necessary to perform visible light irradiation twice. From the viewpoint of reducing the burden on the patient and simplifying the repair work, the number of times of visible light irradiation may be reduced. desirable.

  However, when a conventional adhesive and a photopolymerizable composite resin are used in combination, the adhesive is applied to the cavity surface and filled with the composite resin without substantially irradiating visible light. Even if the composite resin is cured by irradiation, the adhesion strength of the cavity surface to the tooth is not sufficient. Therefore, as a dental filling kit having sufficient adhesive strength even by one-stage light irradiation, for example, Patent Document 1 listed below includes a dental composite resin containing a specific blending amount of an acidic group-containing monomer and Dental filling kits that combine a specific blend of bonding materials have been proposed. Patent Document 2 discloses a dental treatment comprising a pretreatment material containing a radical polymerizable monomer containing an acidic group and water, and a filling restorative material containing an acid group-free and water-soluble radical polymerizable monomer. Filling and repair kits have been proposed. Here, in the dental filling / restoration kit described in Patent Document 2, by blending the vanadium compound in the primer that is the pretreatment material, and by blending the hydroperoxide that is the organic peroxide in the composite resin, It is described that the adhesion between the composite resin and the primer can be made extremely good.

JP 2006-131621 A International Publication No. 2008/149929 Pamphlet

  However, in the dental filling kit described in Patent Document 1, when the adhesive and the composite resin are polymerized and cured by one-step light irradiation, the polymerization reaction proceeds only by photopolymerization. In addition, since the composite resin itself has a low visible light transmittance, there is a problem that the adhesive strength is not sufficient for the bottom of the cavity and the tooth of the cavity wall where the visible light does not reach sufficiently.

  Further, in the dental filling and repair kit described in Patent Document 2, since the chemical polymerization of the primer and the composite resin is low, the visible light is sufficient when the adhesive and the composite resin are polymerized and cured by one-stage light irradiation. There is a problem that the adhesive strength is not sufficient for the bottom of the cavity and the tooth of the cavity wall that do not reach the surface.

  Therefore, when the dental adhesive and the dental composite resin are polymerized and cured by one-step light irradiation, the present invention also applies to the bottom of the cavity and the tooth structure of the cavity wall where visible light does not reach sufficiently. It is an object of the present invention to provide a dental filling kit composed of a dental adhesive and a dental composite resin, which can provide sufficient adhesive strength.

  The present invention that has achieved the above object comprises an acidic group-containing polymerizable monomer (a), water (b), and a dental adhesive (A) containing an amine-based reducing agent (c) and an acidic group. A dental filling kit containing a polymerizable monomer (d), an inorganic peroxide (e), a photopolymerization initiator (f), and a dental composite resin (B) containing a filler (g) .

  The inorganic peroxide (e) is in a powder form, and the average particle diameter of the powder is preferably 0.01 to 100 μm. The inorganic peroxide (e) is preferably peroxodisulfate.

  The dental composite resin (B) preferably further contains a polymerization accelerator (h). The polymerization accelerator (h) is preferably a reducing inorganic compound containing an aromatic sulfinic acid and a salt thereof and / or sulfur. It is preferable that at least a part of the polymerization accelerator (h) is dispersed in a powder form in the dental composite resin (B).

  In filling and restoration using a dental adhesive and a dental composite resin, when the dental filling kit of the present invention is used, visible light does not reach sufficiently when irradiated by an irradiator, and the dental properties of the cavity and the wall of the cavity On the other hand, sufficient adhesive strength can be obtained by one-step light irradiation.

  The present inventors have a dental adhesive comprising a specific component structure containing an amine compound that is a reducing agent for a redox polymerization initiator, and a specific component containing an inorganic peroxide as an oxidizing agent for the redox polymerization initiator. Adopting a filling kit including a dental composite resin composed of a structure enables sufficient adhesive strength to be obtained by one-stage light irradiation even at the bottom of the cavity and the cavity wall where sufficient visible light does not reach. As a result, the present invention has been completed.

  When the dental filling kit of the present invention is applied to the cavity, first, when a dental adhesive is applied to the tooth, the depolymerization by the acidic group-containing polymerizable monomer causes the start of the polymerizable monomer component and redox polymerization. The adhesive component containing the amine-based reducing agent of the agent penetrates into the tooth, and a layer in which the adhesive component and moisture in the tooth are mixed is formed on the surface layer. Next, when the dental composite resin is filled into the cavity, the inorganic peroxide dispersed in the composite resin is dissolved in the layer formed on the surface layer of the tooth, and the concentration is increased. As a result, the amine-based reducing agent and the inorganic peroxide meet in a molecular state at the adhesion interface, and the redox reaction proceeds. For this reason, it is considered that the polymerization reaction by chemical polymerization proceeds at the adhesion interface portion where the adhesive and the composite resin are in contact with each other even when visible light does not reach sufficiently, and expresses excellent adhesiveness. In the above, the dispersion of the inorganic peroxide means a state in which at least a part thereof is present in a solid form in the composite resin, and the dissolution means that it is mixed with water in the composition to form a liquid phase. The state that is.

  The dental filling kit of the present invention includes a dental adhesive and a dental composite resin, which are packaged separately.

<Dental adhesive constituting the dental filling kit of the present invention>
The dental adhesive (A) constituting the dental filling kit of the present invention contains an acidic group-containing polymerizable monomer (a), water (b), and an amine-based reducing agent (c).

  The acidic group-containing polymerizable monomer (a) has a decalcifying action for dissolving the dentin surface, a penetrating action for penetrating into dentin collagen, and a hardening action for forming a hybrid layer with collagen. As the acidic group-containing polymerizable monomer (a) in the dental adhesive (A), an acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, or a carboxylic acid group is used. Examples thereof include polymerizable monomers having at least one and having at least one polymerizable group such as acryloyl group, methacryloyl group, vinyl group, and styrene group. Specific examples of the acidic group-containing polymerizable monomer (a) will be described below. In the following description, (meth) acrylic is a generic term for methacrylic and acrylic.

  Examples of phosphoric acid group-containing polymerizable monomers include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate. 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydro Genphosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyl Xiundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyicosyl dihydrogen phosphate, bis [2- (Meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meta ) Acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyloxydeci ] Hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate And bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate and acid chlorides, alkali metal salts and ammonium salts thereof.

  Examples of pyrophosphate group-containing polymerizable monomers include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], and bis [6- (meth) acryloyl pyrophosphate. Examples include oxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

  Examples of the thiophosphate group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl dihydrogen thiophosphate, 3- (meth) acryloyloxypropyl dihydrogen thiophosphate, 4- (meth) acryloyloxybutyl dihydro Genthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate, 8- (meta ) Acrylyloxyoctyl dihydrogenthiophosphate, 9- (meth) acryloyloxynonyl dihydrogenthiophosphate, 10- (meth) acryloyloxydecyl dihydrogenthio Sulfate, 11- (meth) acryloyloxyundecyl dihydrogen thiophosphate, 12- (meth) acryloyl oxide decyl dihydrogen thiophosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen thiophosphate, 20- (meth) ) Acrylyloxyicosyl dihydrogen thiophosphate and acid chlorides, alkali metal salts and ammonium salts thereof are exemplified.

  Examples of the phosphonic acid group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl phenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, and 6- (meth) acryloyloxyhexyl-3. -Phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl-3- Illustrative are phosphonoacetates and their acid chlorides, alkali metal salts and ammonium salts.

  Examples of the sulfonic acid group-containing polymerizable monomer include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth) acrylate.

  Examples of the carboxylic acid group-containing polymerizable monomer include a polymerizable monomer having one carboxyl group in the molecule and a polymerizable monomer having a plurality of carboxyl groups in the molecule.

  Examples of the polymerizable monomer having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, O- (meth) acryloyl tyrosine, N- (Meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meta ) Acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) Methacryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydro Gemma rate and acid halides are exemplified.

  Examples of the polymerizable monomer having a plurality of carboxyl groups in the molecule include 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid, 10 -(Meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) acryloyloxidedecane-1,1-dicarboxylic acid, 13- ( (Meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxybutyl trimellitate Tate, 4- (meth) acryloyloxyhexyl trimellitate, 4 (Meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3 ′-(meth) acryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate and acid anhydrides thereof Or an acid halide is illustrated.

  One kind of the acidic group-containing polymerizable monomer may be used alone, or a plurality of kinds may be used in combination. Among these acidic group-containing polymerizable monomers, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 1,3-di (meta) is used because of its high adhesive strength when used as a dental adhesive. ) Acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxyethyl trimellitate, 2- (Meth) acrylamido-2-methylpropanesulfonic acid and 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid are preferred.

  The compounding amount of the acidic group-containing polymerizable monomer is preferably 1 to 50 parts by weight, preferably 5 to 40 parts by weight in 100 parts by weight of the total amount of polymerizable monomer components in the dental adhesive (A). More preferably, it is 10 to 30 parts by weight. When the blending amount of the acidic group-containing polymerizable monomer is 1 part by weight or more, good adhesive strength is obtained, and the blending amount of the acidic group-containing polymerizable monomer is 50 parts by weight or less. The polymerizability of the dental adhesive is moderate and the adhesive strength is also kept good.

  Water (b) used for the dental adhesive (A) promotes decalcification action on the tooth by the acidic group-containing polymerizable monomer (a). Moreover, it has a role which melt | dissolves the inorganic peroxide (e) contained in dental composite resin (B). As the water (b), it is necessary to use water that does not substantially contain impurities that adversely affect adhesiveness, and distilled water or ion-exchanged water is preferable. In both cases where the amount of water (b) is too large or too small, the adhesive strength may decrease, and the amount is in the range of 1 to 70% by weight based on the total weight of the dental adhesive (A). Is preferable, the range of 2 to 50% by weight is more preferable, and the range of 5 to 20% by weight is most preferable.

  The amine-based reducing agent (c) is a reducing agent for the redox polymerization initiator. When the dental filling kit of the present invention is used, the inorganic peroxide (e) contained in the dental composite resin (B). It causes a redox reaction at the adhesion interface and contributes to the expression of adhesiveness. Examples of the amine reducing agent (c) include aliphatic amines and aromatic amines.

  Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N- Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl (meth) acrylate, N-methyldiethanolamine di (meth) acrylate, N-ethyldiethanolamine di (meth) Examples thereof include tertiary aliphatic amines such as acrylate, triethanolamine tri (meth) acrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, tertiary aliphatic amines are preferable from the viewpoint of redox reactivity, and among them, N-methyldiethanolamine, triethanolamine, and 2- (dimethylamino) ethyl methacrylate are particularly preferable.

  Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-bis (2 -Hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N- Bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl) -3, 5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, -Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl Examples are -4-t-butylaniline and N, N-dimethyl-3,5-di-t-butylaniline. Among these, N, N-di (2-hydroxyethyl) -p-toluidine is preferable from the viewpoint of redox reactivity.

  Each of the above aliphatic amines and aromatic amines may be used alone or in combination of two or more. The compounding amount of the amine-based reducing agent (c) is preferably 0.01 to 15% by weight, more preferably 0.05 to 10% by weight, based on the total weight of the dental adhesive (A). Most preferred is ˜5 wt%. If the blending amount is less than 0.01% by weight, the adhesive strength of the resulting dental filling kit to the tooth substance may be reduced. On the other hand, when the blending amount exceeds 15% by weight, the color tone stability after the dental adhesive (A) is cured may be lowered.

  The dental adhesive (A) may further contain a polymerizable monomer (d) having no acidic group as long as the effects of the present invention are not hindered. As the polymerizable monomer having no acidic group, a radical polymerizable monomer having a polymerizable group is preferable. From the viewpoint of easy radical polymerization, the polymerizable group may be a (meth) acryl group and / or (meta). ) An acrylamide group is preferred. Although the dental adhesive of the present invention is used in the oral cavity, the oral cavity is a moist environment, and there is a possibility that the polymerizable group may be detached due to hydrolysis or the like. In consideration of irritation, the polymerizable group is preferably a methacryl group and / or a methacrylamide group. Examples of the polymerizable monomer having no acidic group include a water-soluble polymerizable monomer and a hydrophobic polymerizable monomer.

  The water-soluble polymerizable monomer means one having a solubility in water at 25 ° C. of 10% by weight or more. Those having a solubility of 30% by weight or more are preferred, and those having solubility in water at an arbitrary ratio at 25 ° C. are more preferred. The water-soluble polymerizable monomer promotes the penetration of the components of the dental adhesive (A) into the tooth, and also penetrates into the tooth and adheres to the organic component (collagen) in the tooth. Examples of water-soluble polymerizable monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2 , 3-dihydroxypropyl (meth) acrylate, 2-trimethylammonium ethyl (meth) acryl chloride, polyethylene glycol di (meth) acrylate (having 9 or more oxyethylene groups).

  Examples of the hydrophobic polymerizable monomer include crosslinkable polymerizable monomers having a solubility in water at 25 ° C. of less than 10% by weight, and include aromatic compound-based bifunctional polymerizable monomers and aliphatic compounds. Examples thereof include a compound-based bifunctional polymerizable monomer and a trifunctional or higher functional polymerizable monomer. The hydrophobic polymerizable monomer improves the mechanical strength and handleability of the dental adhesive (A).

  Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (commonly referred to as “Bis-GMA”), 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (Meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) ) Propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2 -(4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) Propane, 1,4-bis (2- (meth) acryloylo Shiechiru) pyromellitate, and the like. Among these, 2,2-bis [4- (3- (methacryloyloxy) -2-hydroxypropoxyphenyl] propane and 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane are preferable.

  Examples of aliphatic compound-based bifunctional polymerizable monomers include erythritol di (meth) acrylate, sorbitol di (meth) acrylate, mannitol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol Di (meth) acrylate, glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (common name) “UDMA”), 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane and the like. Among these, glycerol dimethacrylate, triethylene glycol di (meth) acrylate, neopentyl glycol dimethacrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate and 1,2-bis (3 -Methacryloyloxy-2-hydroxypropyloxy) ethane is preferred.

  Examples of trifunctional or higher polymerizable monomers include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) Examples include bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

  Any of the above polymerizable monomers having no acidic group (water-soluble polymerizable monomer and hydrophobic polymerizable monomer) may be used alone or in combination of two or more. May be. When a water-soluble polymerizable monomer is used in the dental adhesive (A), the polymerizable monomer in the dental adhesive (A) is used from the viewpoint of obtaining a good balance between penetration into the tooth and adhesion durability. In the total amount of components of 100 parts by weight, a range of 10 to 98 parts by weight is preferable, a range of 50 to 95 parts by weight is more preferable, and a range of 70 to 90 parts by weight is most preferable. When the dental adhesive (A) contains a hydrophobic polymerizable monomer, phase separation between the hydrophobic polymerizable monomer and water (b) may occur. It is preferable to use a monomer in combination. In this case, the blending amount of the water-soluble polymerizable monomer is preferably in the range of 10 to 90 parts by weight in 100 parts by weight of the total amount of the polymerizable monomer components in the dental adhesive (A). The range of parts by weight is more preferable, and the range of 20 to 50 parts by weight is most preferable. The amount of the hydrophobic polymerizable monomer is preferably 10 to 50 parts by weight in 100 parts by weight of the total amount of polymerizable monomer components in the dental adhesive (A). It is more preferably part by weight, and further preferably 20 to 40 parts by weight.

  A known photopolymerization initiator may be further added to the dental adhesive (A) in order to improve the adhesive force with the tooth. Examples of the photopolymerization initiator include α-diketones, ketals, thioxanthones, acylphosphine oxides, and α-aminoacetophenones.

  Specific examples of α-diketones include camphorquinone, benzyl, and 2,3-pentanedione.

  Specific examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  Specific examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

  Specific examples of acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, dibenzoylphenylphosphine oxide, and bis (2,6-dimethoxy). Benzoyl) phenylphosphine oxide, tris (2,4-dimethylbenzoyl) phosphine oxide, tris (2-methoxybenzoyl) phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2, 3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis (2,6-dimethylphenyl) phosphine oxide, 2,4,6- Water-soluble acylphosphine oxide compounds trimethyl benzoyl ethoxyphenyl phosphine oxide and KOKOKU 3-57916 Patent Publication discloses the like.

  Specific examples of α-aminoacetophenones include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-2-diethylamino-1- (4-morpholinophenyl). ) -Butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -propanone-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -pentanone-1, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -pentanone-1.

  One type of photopolymerization initiator may be used alone, or a plurality of types may be used in combination. The blending amount of the photopolymerization initiator is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of polymerizable monomers in the dental adhesive (A). A range of parts is more preferred.

  Moreover, in order to improve photocurability, you may use together photopolymerization initiators and polymerization accelerators, such as aldehydes and a thiol compound. Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid. These polymerization accelerators may be used alone or in combination of two or more.

  The dental adhesive (A) may further contain a water-soluble volatile organic solvent in order to improve adhesive strength, applicability, and penetration into the tooth. As the water-soluble volatile organic solvent, the boiling point under normal pressure is usually 150 ° C. or less, and the solubility in water at 25 ° C. is 5% by weight or more, more preferably 30% by weight or more, and most preferably at any ratio. An organic solvent that is soluble in water is used. Among these, a water-soluble volatile organic solvent having a boiling point of 100 ° C. or lower under normal pressure is preferable. Specific examples thereof include ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1, Examples include 2-diethoxyethane and tetrahydrofuran.

  One type of water-soluble volatile organic solvent may be blended, or a plurality of types may be blended. If the amount of the water-soluble volatile organic solvent is excessive, the adhesive strength may be reduced. The blending amount of the water-soluble volatile organic solvent is preferably 1 to 50% by weight, more preferably 5 to 40% by weight based on the total weight of the dental adhesive (A), and 10 to 30% by weight. % Range is most preferred.

  The dental adhesive (A) may further contain a known filler such as an inorganic filler, an organic filler, and a composite filler of an inorganic filler and an organic filler. Among these, fine particle silica having a primary particle size of 0.001 to 0.1 μm is preferably used in terms of adhesive strength and applicability. Examples of commercially available products include “Aerosil OX50”, “Aerosil 50”, “Aerosil 200”, “Aerosil 380”, “Aerosil R972”, “Aerosil 130” (all of which are manufactured by Nippon Aerosil Co., Ltd., trade names). . The blending amount of the filler is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the total weight of the dental adhesive (A).

<Dental composite resin constituting the dental filling kit of the present invention>
The dental composite resin (B) constituting the dental filling kit of the present invention includes a polymerizable monomer having no acidic group (d), an inorganic peroxide (e), a photopolymerization initiator (f), and Contains filler (g).

  As the polymerizable monomer (d) having no acidic group, the aforementioned water-soluble polymerizable monomer and hydrophobic polymerizable monomer (aromatic compound-based bifunctional) in the dental adhesive (A). Polymerizable monomer, aliphatic compound-based bifunctional polymerizable monomer, trifunctional or higher functional polymerizable monomer), and the same examples can be given as specific examples and suitable ones.

  The polymerizable monomer (d) having no acidic group may be used alone, but the mechanical strength, handleability, transparency, and dental properties of the resulting dental composite resin (B) From the viewpoint of affinity and adhesiveness with the adhesive (A), aromatic compound-based bifunctional polymerizable monomer, water-soluble polymerizable monomer, and / or aliphatic compound-based bifunctional It is preferable to use a polymerizable polymerizable monomer in combination. The ratio in the case of using them together is not particularly limited, but in the 100 parts by weight of the total amount of the polymerizable monomer component in the dental composite resin (B), the blending of the aromatic compound-based bifunctional polymerizable monomer The amount is preferably 40 to 90 parts by weight, more preferably 50 to 85 parts by weight, and even more preferably 55 to 80 parts by weight.

  The inorganic peroxide (e) is preferably dispersed in powder form in the dental composite resin (B). The powdery inorganic peroxide (e) is dissolved in the water (b) contained in the dental adhesive (A) and the moisture in the tooth, and the amine-based reducing agent contained in the dental adhesive (A). (C) causes a redox reaction at the bonding interface and contributes to the development of adhesiveness. As the inorganic peroxide (e), an inorganic peroxide (e) having a solubility in water at room temperature (25 ° C.) of 0.1 g / 100 mL or more is preferable. When the solubility is less than 0.1 g / 100 mL, when the dental composite resin (B) is applied to the tooth substance coated with the dental adhesive (A), the inorganic peroxide (e) at the adhesion interface portion Is not sufficiently dissolved, and as a result, there is a possibility that the polymerization curability at the adhesion interface portion cannot be improved.

  Examples of the inorganic peroxide (e) include peroxodisulfate and peroxodiphosphate, and among these, peroxodisulfate is preferable from the viewpoint of redox reactivity. Specific examples of peroxodisulfate include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate.

  One kind of the peroxodisulfate may be used alone, or a plurality of kinds may be used in combination. Among the above peroxodisulfates, sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate are preferable.

  Since the inorganic peroxide (e) has a risk that the aesthetics and mechanical strength of the dental composite resin (B) obtained if the particle size is excessively large, the average particle size is preferably 100 μm or less. 50 μm or less is more preferable, and 20 μm or less is more preferable. However, if the average particle diameter is too small, the specific surface area of the powder becomes excessive and the amount dispersible in the dental composite resin (B) decreases, so the average particle diameter is preferably 0.01 μm or more. That is, the average particle diameter of the inorganic peroxide (e) is preferably in the range of 0.01 to 100 μm, more preferably in the range of 0.01 to 50 μm, and still more preferably in the range of 0.01 to 20 μm. The average particle diameter of the inorganic peroxide (e) refers to the volume average particle diameter, and the volume average particle diameter is, for example, image analysis software (for example, based on an electron micrograph of 100 particles or more) And Mac-View; manufactured by Mountec Co., Ltd.).

  The shape of the inorganic peroxide (e) includes various shapes such as a spherical shape, a needle shape, a plate shape, and a crushed shape, but is not particularly limited. The inorganic peroxide (e) can be produced by a conventionally known method such as a pulverization method, a freeze-drying method, or a reprecipitation method.

  The blending amount of the inorganic peroxide (e) is preferably 0.1 to 10% by weight based on the total weight of the dental composite resin (B). If the blending amount is less than 0.1% by weight, the adhesive strength of the resulting dental filling kit to the tooth substance may be reduced. On the other hand, when the blending amount exceeds 10% by weight, the mechanical strength and transparency of the dental composite resin (B) may be lowered.

  Examples of the photopolymerization initiator (f) in the dental composite resin (B) include α-diketones, ketals, thioxanthones, acylphosphine oxides, α-aminoacetophenones, and the like. Specific examples of these photopolymerization initiators (f) are the same as the aforementioned α-diketones, ketals, thioxanthones, acylphosphine oxides, α-aminoacetophenones in the dental adhesive (A). Are illustrated.

  One type of photopolymerization initiator (f) may be used alone, or a plurality of types may be used in combination. The blending amount of the photopolymerization initiator is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of polymerizable monomers in the dental composite resin (B), and is 0.1 to 3 parts by weight. A range of parts is more preferred.

  Moreover, in order to improve photocurability, you may use together a photoinitiator (f), aldehydes, a thiol compound, the aromatic amine which has an electron withdrawing group, etc. Aromatic tertiary amines having electron withdrawing groups do not have sufficient reducing properties to initiate redox polymerization, but can promote photoradical polymerization. Specific examples of the aldehydes and thiol compounds include the same aldehydes and thiol compounds as described above. As an aromatic tertiary amine having an electron-withdrawing group, an aromatic ring hydrogen atom of the aromatic tertiary amine is an electron such as a carboxylic acid group, a carboxylic acid ester group, an acyl group, a nitrile group, or a halogen group. Examples include compounds substituted with an attractive group. Specific examples include ethyl 4-N, N-dimethylaminobenzoate, methyl 4-N, N-dimethylaminobenzoate, 4-N, N-dimethylaminobenzoate. Examples include propyl acid, n-butoxyethyl 4-N, N-dimethylaminobenzoate, 2- (methacryloyloxy) ethyl 4-N, N-dimethylaminobenzoate, 4-N, N-dimethylaminobenzophenone, and the like. These compounds may be used alone or in combination of two or more.

  The filler (g) improves the handleability, radiopacity, mechanical strength and the like of the dental composite resin (B). Examples of the filler (g) include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers. A filler (g) may mix | blend 1 type individual, and may mix | blend multiple types in combination.

As the inorganic filler, silica; minerals based on silica such as kaolin, clay, mica, mica; silica based, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, La Examples thereof include ceramics and glasses containing ₂ O ₃ , SrO, ZnO, CaO, P ₂ O ₅ , Li ₂ O, Na ₂ O and the like. As the glass, lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass are preferably used. Crystal quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride are also preferably used It is done.

  Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymer, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

  Examples of composite fillers of inorganic fillers and organic fillers include inorganic fillers dispersed in organic fillers and inorganic / organic composite fillers in which inorganic fillers are coated with various polymers.

  In order to improve curability, mechanical strength, and coatability, the filler (g) may be used after surface treatment with a known surface treatment agent such as a silane coupling agent in advance. As the surface treatment agent, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Examples are mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

  The blending amount of the filler (g) is preferably 30 to 90% by weight, more preferably 40 to 90% by weight, and 50 to 85% by weight based on the total weight of the dental composite resin (B). A range is most preferred.

  In the dental filling kit of the present invention, it is preferable to further blend a polymerization accelerator (h) with the dental composite resin (B) in order to improve the polymerization curability at the adhesive interface. As the polymerization accelerator (h), aromatic sulfinic acid and salts thereof, sulfur-containing reducing inorganic compounds, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes Thiol compounds, thiourea compounds, and thiourea compounds.

  Examples of aromatic sulfinic acid and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, Sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfate, 2,4,6-trimethyl Potassium benzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, 2,4,6 -Sodium triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-tri Isopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, 2,4,6- Examples include calcium triisopropylbenzenesulfinate.

  Reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, dithionites, etc. Among them, sulfites and bisulfites are mentioned. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite and the like.

  As the borate compound, an aryl borate compound is preferable. Specific examples of suitably used aryl borate compounds include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluoro) as borate compounds having one aryl group in one molecule. Phenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl ] Boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butyloxy) Phenyl) boron, trialkyl (m-butyloxyphenyl) boron, Alkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl, n-dodecyl, etc.) And salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt) , Ethyl quinolinium salt, butyl quinolinium salt, etc.).

  Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5-bistrifluoromethyl) phenyl. Boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitro Phenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) Boron and di Rualkyldi (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group and n-dodecyl group) and salts thereof (sodium salt, lithium salt) Salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium Salt).

  Further, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3 , 5-Bistrifluoromethyl) phenyl boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltri ( p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butyloxyphenyl) Boron, monoalkyltri (m-butyloxyphenyl) boron, monoal Rutri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (the alkyl group is one selected from n-butyl group, n-octyl group, n-dodecyl group, etc.) and Their salts (sodium, lithium, potassium, magnesium, tetrabutylammonium, tetramethylammonium, tetraethylammonium, methylpyridinium, ethylpyridinium, butylpyridinium, methylquinolinium, Norinium salts, butylquinolinium salts, etc.).

  Further, borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron. Tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) ) Boron, Tetrakis (p-butylphenyl) boron, Tetrakis (m-butylphenyl) boron, Tetrakis (p-butyloxyphenyl) boron, Tetrakis (m-butyloxyphenyl) boron, Tetrakis (p-octyloxyphenyl) boron , Tetrakis (m-octyloxyf Nyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, ( p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron, and their salts (sodium, lithium, potassium, magnesium, tetra Butylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.).

  Examples of barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, and 5-ethylbarbituric acid. Acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbi Tool acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, Benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutyl Barbituric acid, 1,3-diethyl-5-butyl barbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and salts thereof (alkali metal or alkaline earth metal) Examples of salts of these barbituric acids include If, sodium 5-butyl barbituric acid, 1,3,5-trimethyl barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric sodium tools acids and the like.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis ( Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p Bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (o-methoxyphenyl) ethenyl] -4,6 -Bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4- Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ethoxy] -4,6-bis (trichloromethyl)- Examples include s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, and the like.

  As the copper compound, for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  Examples of the tin compound include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Among these, suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

  The vanadium compound is preferably an IV valent and / or V valent vanadium compound. Examples of the IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1- Japanese Patent Application Laid-Open Publication No. 2003, such as phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V) The compound described in -96122 is mentioned.

  As the halogen compound, for example, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like are preferably used.

  Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like.

  Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  Examples of the thiourea compound include 1- (2-pyridyl) -2-thiourea, ethylenethiourea, thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′-diethylthiourea, N , N′-di-n-propylthiourea, N, N′-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra- Examples include n-propylthiourea and tetracyclohexylthiourea.

  These polymerization accelerators (h) may be used alone or in combination of two or more. Among these polymerization accelerators (h), the aromatic sulfinic acid and the point that the stability of the components in the dental composite resin (B) and the adhesion strength to the tooth of the resulting dental filling kit are large. Preferred is a reducing inorganic compound containing a salt thereof and / or sulfur, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, sodium sulfite, potassium sulfite, calcium sulfite More preferably, it is at least one selected from the group consisting of ammonium sulfite, sodium hydrogen sulfite, and potassium hydrogen sulfite.

  It is preferable that at least a part of these polymerization accelerators (h) is dispersed in a powder form in the dental composite resin (B). When the dental composite resin (B) is applied to the dental material coated with the dental adhesive (A) by dispersing the polymerization accelerator (h) in powder, the polymerization accelerator (h) is bonded to the adhesive interface portion. Therefore, the polymerization curability at the bonding interface can be further increased. In addition, since the polymerization accelerator (h) has a possibility that the aesthetics and mechanical strength of the dental composite resin obtained when the particle size is excessively large, the average particle size is preferably 500 μm or less, preferably 100 μm or less. Is more preferable, and 50 μm or less is more preferable. However, if the average particle size is too small, the specific surface area of the powder becomes excessive and the handling property of the dental composite resin may be lowered. Therefore, the average particle size is preferably 0.01 μm or more. That is, the average particle diameter when dispersed in powder is preferably in the range of 0.01 to 500 μm, more preferably in the range of 0.01 to 100 μm. The average particle diameter of the polymerization accelerator (h) refers to the volume average particle diameter. The volume average particle diameter is, for example, image analysis software (for example, based on an electron micrograph of 100 or more particles). Mac-View; manufactured by Mountec Co., Ltd.) can be calculated by performing image analysis.

  The shape in the case of dispersing the polymerization accelerator (h) in powder includes various shapes such as a spherical shape, a needle shape, a plate shape, and a crushed shape, but is not particularly limited. As the polymerization accelerator (h), a fine powder can be produced by a conventionally known method such as a pulverization method or a freeze-drying method.

  The blending amount of the polymerization accelerator (h) is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, based on the total weight of the dental composite resin (B), and 0.3 to 3% by weight is most preferred. If the blending amount is less than 0.1% by weight, the adhesive strength of the resulting dental filling kit to the tooth substance may be reduced. On the other hand, when the blending amount exceeds 10% by weight, the mechanical strength of the obtained dental composite resin may be lowered.

  In the dental filling kit of the present invention, the dental adhesive (A) and / or the dental composite resin (B) is further provided with a fluorine ion releasing substance for the purpose of imparting acid resistance to the tooth. You may mix | blend. Fluorine ion releasing substances include fluorine ion releasing polymers such as a copolymer of methyl methacrylate and methacrylic fluoride, fluorine ion releasing substances such as cetylamine hydrofluoride, and the above-described fluoro as an inorganic filler. Examples include aluminosilicate glass, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride and the like.

  Further, the dental adhesive (A) and / or the dental composite resin (B) may further contain additives such as a stabilizer (polymerization inhibitor), a colorant, a fluorescent agent, and an ultraviolet absorber. . Also, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride, (meth) acryloyloxydecylammonium chloride, and triclosan Good.

  Next, an example of a method for using the dental filling kit according to the present invention will be described. First, the dental adhesive (A) is applied to the cavity to be treated using a sponge or brush, and in that state, 0 to 120 seconds, preferably 1 to 60 seconds, more preferably 5 to 30 seconds, most preferably Leave for 10 to 20 seconds, or continue rubbing within 60 seconds using a sponge or the like on the tooth surface. Next, air blow is performed using a dental air syringe as necessary, and then the dental composite resin (B) is placed and filled in the cavity. At this time, the usage of the composite resin is not particularly limited. Generally, it is arranged with a spatula or the like and arranged in the same shape as an actual tooth. Finally, the filling and repairing operation can be completed by irradiating the filling and repairing portion with visible light using a dental visible light irradiator.

  Since the dental filling kit of the present invention uses redox polymerization (chemical polymerization) in addition to photopolymerization, when irradiated by an irradiator, visible light does not reach the bottom of the cavity and the tooth quality of the cavity wall. On the other hand, sufficient adhesive strength can be obtained by one-stage light irradiation.

  The present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. Abbreviations used below are as follows.

[Acid group-containing polymerizable monomer (a)]
MDP: 10-methacrylolyloxydecyl dihydrogen phosphate 4META: 4-methacryloyloxyethyl trimellitate anhydride

[Amine reducing agent (c)]
DEPT: N, N-bis (2-hydroxyethyl) -p-toluidine TEA: triethanolamine DMAEMA: 2- (dimethylamino) ethyl methacrylate

[Polymerizable monomer having no acidic group (d)]
Water-soluble polymerizable monomer:
HEMA: 2-hydroxyethyl methacrylate Hydrophobic polymerizable monomer:
Bis-GMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane D-2.6E: 2,2-bis (methacryloyloxypolyethoxyphenyl) propane 3G: triethylene glycol Dimethacrylate NPG: Neopentyl glycol dimethacrylate

[Powdered inorganic peroxide (e)]
KPS: potassium peroxodisulfate NaPS: sodium peroxodisulfate

[Photopolymerization initiator (f)]
CQ: camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide DABB: n-butoxyethyl 4-N, N-dimethylaminobenzoate (polymerization accelerator for photopolymerization initiator)

[Filler (g)]
R972: Silica (made by Nippon Aerosil Co., Ltd., trade name “Aerosil R972”)

  Silane-treated quartz powder and silane-treated colloidal silica powder are obtained according to the following production method.

Silane-treated quartz powder:
Quartz (manufactured by MARUWA QUARTZ) was pulverized with a ball mill to obtain quartz powder having an average particle diameter of about 4.5 μm. 100 parts by weight of this quartz powder was subjected to surface treatment with 3 parts by weight of γ-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain a silane-treated quartz powder.

Silane-treated colloidal silica powder:
In 100 parts by weight of distilled water, 0.3 parts by weight of acetic acid and 5 parts by weight of γ-methacryloyloxypropyltrimethoxysilane are added and stirred, and further colloidal silica powder (trade name “Aerosil 130” manufactured by Nippon Aerosil Co., Ltd.) Was added and stirred for 1 hour. After removing water by freeze-drying, heat treatment was performed at 80 ° C. for 5 hours to obtain a silane-treated colloidal silica powder.

[Polymerization accelerator (h)]
TPBSS: sodium 2,4,6-triisopropylbenzenesulfinate

[Others]
BPO: Benzoyl peroxide (organic peroxide)
BHT: 2,6-di-t-butyl-4-methylphenol (stabilizer (polymerization inhibitor))

In addition, the peroxodisulfate marketed as a reagent is a crystalline powder with an average particle diameter of 500-1000 micrometers normally. The fine powdered peroxodisulfate described in the Examples can be obtained by the following methods, respectively.
(Method 1)
A method obtained by preparing an aqueous solution of peroxodisulfate, freezing the aqueous solution at −50 ° C., and then vacuum drying in a frozen state.
(Method 2)
A method in which a saturated aqueous solution of peroxodisulfate is prepared, this aqueous solution is poured into ethanol at 0 ° C., and the resulting crystals are filtered off, washed with ethanol, and then air-dried.
(Method 3)
A method in which a saturated aqueous solution of peroxodisulfate is prepared, this aqueous solution is rapidly cooled to 0 ° C., and the resulting crystals are filtered off and air-dried.
(Method 4)
Method obtained by mechanical grinding and sieving.
In this example, among the methods 1 to 4, fine pulverization by the method 1 was adopted.
The average particle diameter of each peroxodisulfate fine powder and sodium sulfite was subjected to image analysis using image analysis software (Mac-View; manufactured by Mountec) based on an electron micrograph of 100 or more particles. Later, the volume average particle size was calculated.

Example 1
The following dental adhesive and dental composite resin were prepared to prepare a dental filling kit. The dental composite resin (B-1) was prepared by mixing components other than KPS (average particle size: 6.5 μm), silane-treated quartz powder and silane-treated colloidal silica powder, and stirring to obtain a uniform solution. The silane-treated quartz powder and the silane-treated colloidal silica powder were kneaded and defoamed. KPS in the dental composite resin (B-1) was in a dispersed state. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described below.

Dental adhesive (A-1):
MDP 10 parts by weight HEMA 45 parts by weight distilled water 45 parts by weight DEPT 2 parts by weight Dental composite resin (B-1):
Bis-GMA 70 parts by weight 3G 30 parts by weight KPS (average particle size 6.5 μm) 1 part by weight CQ 0.2 part by weight DABB 0.2 part by weight TMDPO 0.5 part by weight BHT 0.05 part by weight Silane-treated quartz powder 288 parts by weight Silane-treated colloidal silica powder 12 parts by weight

[Measurement method of tensile adhesive strength (composite resin thickness 2mm)]
The lip surface of bovine mandibular anterior teeth was polished with silicon carbide paper under running water to expose the flat surface of dentin. The exposed flat surface was further polished with # 1000 silicon carbide paper under running water. After polishing, the surface water was dried by air blowing. An adhesive tape having a round hole with a diameter of 3 mm and having a thickness of about 150 μm was attached to the smooth surface after drying to define the adhesion area. The dental adhesive was applied to the round hole with a brush, allowed to stand for 10 seconds, and then dried using a dental air syringe until the fluidity of the dental adhesive disappeared. Next, a cylindrical polytetrafluoroethylene mold having an inner diameter of 3 mm and a height of 2 mm is placed over the round hole (attachment surface), and a dental composite resin is filled in the cylinder, and a release polyester film Covered. A slide glass was placed on the release polyester film and pressed, and irradiated with light using a dental light irradiator “JETLITE 3000” for 20 seconds to be cured. After light irradiation, the cylindrical polytetrafluoroethylene mold was removed, and the composite resin cured surface from which the release polyester film was peeled off was used as a commercially available dental resin cement (trade name “Panavia 21” manufactured by Kuraray Medical Co., Ltd.). Was used to bond one end face (circular cross section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 mm), and allowed to stand for 30 minutes to obtain a test piece. A total of eight test pieces were produced. Next, the test piece was immersed in distilled water and left in a thermostat set at 37 ° C. for 24 hours, then taken out and measured for tensile adhesive strength. The tensile bond strength was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min. The average value of the measured values of the eight test pieces was taken as the tensile bond strength of the test piece.

(Example 2)
The following dental composite resin (B-2) was prepared and combined with the dental adhesive (A-1) of Example 1 to prepare a dental filling kit. Dental composite resin (B-2) is formulated with components other than KPS (average particle size: 6.5 μm), sodium sulfite (average particle size: 6.1 μm), silane-treated quartz powder, and silane-treated colloidal silica powder. Then, after stirring to obtain a uniform solution, KPS, sodium sulfite, silane-treated quartz powder, and silane-treated colloidal silica powder were kneaded and defoamed. KPS and sodium sulfite in the dental composite resin (B-2) were in a dispersed state. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Dental composite resin (B-2):
Bis-GMA 70 parts by weight 3G 30 parts by weight KPS (average particle size 6.5 μm) 1 part by weight Sodium sulfite 1 part by weight CQ 0.2 part by weight DABB 0.2 part by weight TMDPO 0.5 part by weight BHT 0.05 part by weight Part silane-treated quartz powder 288 parts by weight silane-treated colloidal silica powder 12 parts by weight

(Example 3)
Instead of KPS (1 part by weight) in the dental composite resin (B-2) of Example 2, a dental composite resin (B-3) with NaPS (average particle size 9.3 μm, 1 part by weight) was used. Prepared and made dental filling kit. NaPS and sodium sulfite in the dental composite resin (B-3) were in a dispersed state. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Example 4
Instead of 3G (30 parts by weight) in the dental composite resin (B-2) of Example 2, a dental composite resin (B-4) with HEMA (30 parts by weight) was prepared, and a dental filling kit Was made. KPS and sodium sulfite in the dental composite resin (B-4) were in a dispersed state. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

(Example 5)
Instead of DEPT (2 parts by weight) in the dental adhesive (A-1) of Example 1, a dental adhesive (A-2) as TEA (2 parts by weight) was prepared. A dental filling kit was prepared in combination with the dental composite resin (B-2). With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

(Example 6)
Instead of DEPT (2 parts by weight) in the dental adhesive (A-1) of Example 1, a dental adhesive (A-3) as DMAEMA (2 parts by weight) was prepared. A dental filling kit was prepared in combination with the dental composite resin (B-2). With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

(Example 7)
The following dental adhesive (A-4) was prepared and combined with the dental composite resin (B-2) of Example 2 to prepare a dental filling kit. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Dental adhesive (A-4):
MDP 10 parts by weight HEMA 45 parts by weight distilled water 45 parts by weight DEPT 0.8 parts by weight TEA 1.2 parts by weight

(Example 8)
Instead of MDP (10 parts by weight) in the dental adhesive (A-1) of Example 1, 4META (10 parts by weight) of dental adhesive (A-5) was prepared. A dental filling kit was prepared in combination with the dental composite resin (B-2). With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Example 9
The following dental composite resin (B-5) was prepared and combined with the dental adhesive (A-1) of Example 1 to prepare a dental filling kit. The dental composite resin (B-5) was prepared by mixing components other than KPS (average particle size: 6.5 μm), TPBSS, silane-treated quartz powder, and silane-treated colloidal silica powder, and stirring to obtain a uniform solution. Thereafter, KPS, TPBSS, silane-treated quartz powder, and silane-treated colloidal silica powder were kneaded and defoamed. KPS and TPBSS in the dental composite resin (B-5) were in a dispersed state. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Dental composite resin (B-5):
D-2.6E 70 parts by weight NPG 30 parts by weight KPS (average particle size 6.5 μm) 1 part by weight TPBSS 1 part by weight CQ 0.2 part by weight DABB 0.2 part by weight TMDPO 0.5 part by weight BHT 0.05 Parts by weight silane-treated quartz powder 288 parts by weight silane-treated colloidal silica powder 12 parts by weight

(Example 10)
The following dental adhesive (A-6) was prepared and combined with the dental composite resin (B-1) of Example 1 to prepare a dental filling kit. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Dental adhesive (A-6):
MDP 10 parts HEMA 30 parts Bis-GMA 35 parts distilled water 15 parts DEPT 2 parts ethanol 10 parts CQ 2 parts DABB 1 part TMDPO 2 parts R972 7 parts by weight

(Example 11)
A dental filling kit was prepared by combining the dental adhesive (A-6) of Example 10 and the dental composite resin (B-2) of Example 2. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

(Comparative Example 1)
The following dental adhesive (A-7) was prepared and combined with the dental composite resin (B-2) of Example 2 to prepare a dental filling kit. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Dental adhesive (A-7):
MDP 10 parts by weight HEMA 45 parts by weight distilled water 45 parts by weight

(Comparative Example 2)
The following dental composite resin (B-6) was prepared and combined with the dental adhesive (A-1) of Example 1 to prepare a dental filling kit. The dental composite resin (B-6) was prepared by mixing components other than the silane-treated quartz powder and the silane-treated colloidal silica powder, and stirring to obtain a uniform solution, and then the silane-treated quartz powder and the silane-treated colloidal silica powder. Was prepared by kneading and defoaming. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Dental composite resin (B-6):
Bis-GMA 70 parts by weight 3G 30 parts by weight CQ 0.2 parts by weight DABB 0.2 parts by weight TMDPO 0.5 parts by weight BHT 0.05 parts by weight Silane-treated quartz powder 288 parts by weight Silane-treated colloidal silica powder 12 parts by weight

(Comparative Example 3)
A dental filling kit was prepared by combining the dental adhesive (A-6) of Example 10 and the dental composite resin (B-6) of Comparative Example 2. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

(Comparative Example 4)
The following dental composite resin (B-7) was prepared and combined with the dental adhesive (A-1) of Example 1 to prepare a dental filling kit. The dental composite resin (B-7) was prepared by mixing components other than the silane-treated quartz powder and the silane-treated colloidal silica powder, and stirring to obtain a uniform solution, and then the silane-treated quartz powder and the silane-treated colloidal silica powder. Was prepared by kneading and defoaming. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

Dental composite resin (B-7):
Bis-GMA 70 parts by weight 3G 30 parts by weight BPO 1 part by weight CQ 0.2 part by weight DABB 0.2 part by weight TMDPO 0.5 part by weight BHT 0.05 part by weight Silane-treated quartz powder 288 parts by weight Silane-treated colloidal silica powder 12 parts by weight

(Comparative Example 5)
A dental filling kit was prepared by combining the dental adhesive (A-6) of Example 10 and the dental composite resin (B-7) of Comparative Example 4. With respect to this dental filling kit, the tensile adhesive strength (composite resin thickness 2 mm) was examined by the method described above. The results are shown in Table 1.

  For reference, the components of the dental filling kit of the example are summarized in Table 2, and the components of the dental filling kit of the comparative example are summarized in Table 3. As shown in Table 1, the dental filling kits of the present invention produced in Examples 1 to 11 exhibited high adhesive strength even under conditions where the composite resin had a thickness of 2 mm and visible light did not reach sufficiently. This is presumably because in these dental filling kits, the powdered inorganic peroxide was dissolved and present at a high concentration at the bonding interface, and the polymerization and curing reaction by chemical polymerization proceeded efficiently. On the other hand, the dental filling kits produced in Comparative Examples 1 to 5 had low adhesion strength to dentin. This is presumably because in the dental filling kits of Comparative Examples 1 to 3, the chemical polymerization did not proceed at the bonding interface, and the visible light did not reach sufficiently, so the polymerization curability by photopolymerization was low. In the dental filling kits of Comparative Examples 4 to 5, since BPO is dissolved in the composite resin, the concentration of BPO at the bonding interface does not increase, the degree of progress of chemical polymerization is low, and the visible light is sufficient. This is probably because the polymerization curability by photopolymerization was low because it did not reach.

  The dental filling kit of the present invention is useful for filling and repairing a tooth structure damaged by caries or the like.

Claims (6)

  Dental adhesive (A) containing an acidic group-containing polymerizable monomer (a), water (b), and an amine-based reducing agent (c), and a polymerizable monomer (d) having no acidic group And a dental composite resin (B) containing an inorganic peroxide (e), a photopolymerization initiator (f), and a filler (g).   The dental filling kit according to claim 1, wherein the inorganic peroxide (e) is in a powder form, and the average particle size of the powder is 0.01 to 100 µm.   The dental filling kit according to claim 1 or 2, wherein the inorganic peroxide (e) is peroxodisulfate.   The dental filling kit according to any one of claims 1 to 3, wherein the dental composite resin (B) further contains a polymerization accelerator (h).   The dental filling kit according to claim 4, wherein the polymerization accelerator (h) is a reducing inorganic compound containing an aromatic sulfinic acid and a salt thereof and / or sulfur.   The dental filling kit according to claim 4 or 5, wherein at least a part of the polymerization accelerator (h) is dispersed in powder form in the dental composite resin (B).