Method for manufacturing dental fillings and dental compositions

Abstract

To provide a method for producing a dental filler that prevents a degradation of equipment and shows superior long-term storageability even when used in a dental composition comprising an acidic component.SOLUTION: The present invention provides a method for producing a dental filler comprising inorganic particles comprising a polyvalent metal element. The method includes the step of treating the inorganic particles with a solution comprising a chelator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a method for producing dental filling materials and a dental composition. [Background technology]

[0002] In dental compositions such as dental cements and dental composite resins, fillers containing polyvalent metal elements (including transition metal elements), such as barium glass, are sometimes incorporated to improve mechanical strength and provide radiopaqueness. In recent years, (meth)acrylates having acidic groups, such as MDP, have been incorporated as polymerizable monomers to impart self-adhesion to dental compositions.

[0003] However, when these are combined in the same agent, acid-reactive barium glass and other materials react with acid groups, leading to problems with storage stability, such as a decrease in the reactivity of the composition and gelation. In response to this, a technique has been disclosed for long-term stable storage of a composition by including a step of treating inorganic particles containing polyvalent metals (such as barium glass) with an acid (a strong acid such as hydrochloric acid) (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2011-178778 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In conventional methods for processing inorganic particles, when surface treatment of fillers with acid, equipment such as containers are exposed to the acid. ru There is a problem with deterioration due to corrosion. Furthermore, there are safety concerns for workers when using acid-based treatments.

[0006] An object of the present invention is to provide a method for producing a dental filling material that suppresses deterioration of equipment and has high long-term storage stability even when used in a dental composition containing an acidic component.

Means for Solving the Problems

[0007] A method for producing a dental filling material according to one aspect of the present invention is a method for producing a dental filling material containing inorganic particles containing a polyvalent metal element, wherein the inorganic particles are treated with a solution containing a chelating agent that does not act as an acid aminopolycarboxylate salts and then subjected to a silane treatment.

Effects of the Invention

[0008] According to one aspect of the present invention, it is possible to provide a method for producing a dental filling material that suppresses deterioration of equipment and has high long-term storage stability even when used in a dental composition containing an acidic component.

Mode for Carrying Out the Invention

[0009] Hereinafter, embodiments of the present invention will be described in detail. The method for producing a dental filling material according to the present embodiment is a method for producing a dental filling material containing inorganic particles containing a polyvalent metal element.

[0010] In the present specification, a dental filling material refers to a material used for restorative purposes, for example, a material for filling a cavity in a tooth structure. Inorganic particles refer to particles of a compound of a metal element or a non-metal element, for example, glass particles. Note that metals include metalloids.

[0011] The polyvalent metal element refers to a metal element having an ionic valence of 2 or more, for example, Ca 2+ , Al 3+ , B 3+ , Si 4+ , Bi 5+ and other typical elements, Zn 2+ , Ti 3+ , Y 3+ , Zr 4+ , V 5+They are transition elements such as etc. Note that these polyvalent metal elements may be contained one or more kinds in the inorganic particles.

[0012] The component and quantitative ratio of the inorganic particles are not particularly limited. For example, by mass ratio, Al2O3 but 10%, B2O3 but 10%, BaO but 25%, SiO2 but 55%.

[0013] The manufacturing method of the dental filling material of this embodiment includes a step of treating the inorganic particles with a solution containing a chelating agent.

[0014] In this specification, the chelating agent is a non-metal ligand that forms an ionic bond with a metal in a solution, binds to one metal ion with a plurality of coordination atoms in the ligand molecule, and shows an effect of reducing the activity of the metal ion (hereinafter sometimes referred to as a chelating effect). Note that the chelating agent used in this embodiment does not include a chelating agent that becomes an acid. and

[0015] but The solution containing the chelating agent (hereinafter sometimes referred to as a chelating solution) indicates a solution in which the chelating agent is dissolved in a solvent. Here, the solvent is, for example, water, preferably ion-exchanged water. Note that the pH of the solvent is preferably 6 or more, more preferably pH 6 or more and 9 or less.

[0016] The concentration of the solution containing the chelating agent (chelating solution) is not particularly limited as long as the chelating effect can be obtained. The concentration of the chelating solution is, for example, 0.01 g / L or more, preferably 0.1 g / L or more, more preferably 1 g / L or more. Note that the upper limit of the concentration of the chelating solution is arbitrary, and it may be 100 g / L or less in view of the relationship between the chelating effect and cost.

[0017] ​The chelating agent is not particularly limited, but is preferably an aminopolycarboxylate. Aminopolycarboxylic acid, also called complexan, has at least one amino group diacetate -N(CH2COOH)2 in its compound.

[0018] The aminopolycarboxylate is not particularly limited. Specific examples of aminopolycarboxylates include ethylenediaminetetraacetic acid (EDTA) salts (e.g., EDTA·2Na, EDTA·3Na, EDTA·4Na, etc.), diethylenetriaminepentaacetic acid (DTPA) salts (e.g., DTPA·3Na, DTPA·5Na, etc.), triethylenetetramine-N,N,N',N'',N''',N'''-hexaacetic acid (TTHA) salts (e.g., TTHA·6Na, etc.), hydroxyethyliminodiacetic acid (HIDA) salts (e.g., HIDA·2Na, etc.), nitrilotriacetic acid (NTA) salts (e.g., NTA·3Na, etc.), etc. The salt is not limited to sodium salts and may be, for example, potassium salts.

[0019] These aminopolycarboxylates may be used alone or in combination of two or more. Among these, ethylenediaminetetraacetic acid (EDTA) salts are preferred from the viewpoint of being inexpensive and obtaining a chelating effect.

[0020] The amount of the chelating solution is not particularly limited. For example, the amount of the chelating solution is 4 to 10 times the mass of the inorganic particles to be treated. When the amount of the chelating solution is 4 to 10 times the mass of the inorganic particles to be treated, appropriate treatment of the inorganic particles becomes possible.

[0021] The method for producing the dental filling material of the present embodiment preferably further includes a heat treatment step.

[0022] The heating temperature in the heat treatment step is not particularly limited, but is, for example, 300°C to 700°C. The heating time is not particularly limited, but is, for example, about 30 minutes to 12 hours.

[0023] The method for manufacturing dental fillings according to this embodiment further includes a silane treatment step. Here, silane treatment refers to treating the surface of inorganic particles after treatment with a chelate solution with a silane coupling agent. The silane coupling agent is not particularly limited and may include, for example, organosilicon compounds such as γ-methacryloxypropyltrimethoxysilane. of It is used after being silane-converted by conventional methods.

[0024] According to the method for manufacturing dental fillings of this embodiment, by treating inorganic particles containing polyvalent metal elements with a chelating solution, deterioration of equipment such as processing containers due to oxidation can be suppressed. Furthermore, since no acid is used in this chelating solution treatment, worker safety can be ensured.

[0025] Furthermore, by treating inorganic particles containing polyvalent metal elements with a chelate solution, the polyvalent metals present on the surface of the inorganic particles can be removed. but Chelating agents in Chelate So This suppresses the acid reactivity of inorganic particles. Therefore, even when a dental filling material containing inorganic particles with polyvalent metal elements is used in a dental composition containing acidic components, the long-term shelf life of the dental composition can be improved.

[0026] In the method for manufacturing dental fillings according to this embodiment, as described above, by using an aminopolycarboxylate as a chelating agent, it is possible to suppress deterioration of equipment such as processing containers due to oxidation. Furthermore, even when a dental filling containing inorganic particles including polyvalent metal elements is used in a dental composition containing acidic components, it is possible to improve the long-term shelf life of the dental composition.

[0027] In the method for manufacturing dental fillings of this embodiment, ethylenediaminetetraacetic acid (EDTA) salt is further used as the aminopolycarboxylate salt. Since EDTA salt is readily available at low cost on the market, using such an EDTA salt makes it possible to suppress the deterioration of the equipment due to oxidation and to improve the long-term shelf life of dental fillings that contain inorganic particles containing polyvalent metal elements in dental compositions containing acidic components, all at a low cost.

[0028] In the manufacturing method of dental fillings according to this embodiment, the inclusion of a heat treatment step further improves chemical stability and corrects distortion of inorganic particles after treatment with a chelating solution. Therefore, the long-term storage properties of dental fillings containing inorganic particles containing polyvalent metal elements can be further improved when used in dental compositions containing acidic components.

[0029] In the method for manufacturing dental fillings of this embodiment, by further including a silane treatment step, the surface of the inorganic particles after treatment with the chelate solution can be made hydrophobic by silane treatment. This improves the wettability of the inorganic particles containing polyvalent metal elements to the resin material, and improves the affinity with dental compositions containing resin and the like.

[0030] The dental filling material of this embodiment is manufactured by the method for manufacturing dental filling materials described above. As a result, the dental filling material of this embodiment retains the effects obtained by the method for manufacturing dental filling materials described above. Specifically, the dental filling material of this embodiment is obtained by treating inorganic particles containing polyvalent metal elements with a chelate solution, thereby suppressing deterioration due to oxidation of equipment such as processing containers, and ensuring the safety of workers.

[0031] As described above, the dental filling material of this embodiment suppresses the acid reactivity of inorganic particles, and therefore, even when used in a dental composition containing acidic components, it can improve the long-term shelf life of the dental composition.

[0032] The dental composition according to this embodiment contains a dental filling material manufactured by the method for manufacturing dental filling materials described above. As a result, the dental composition of this embodiment provides the same effects obtained by the method for manufacturing dental filling materials described above.

[0033] Specifically, in the dental composition according to this embodiment, since no acid is used to treat the inorganic particles containing polyvalent metal elements in the dental filling material contained in the dental composition, deterioration due to oxidation of equipment can be suppressed, and the safety of workers can be ensured.

[0034] Furthermore, in the dental composition according to this embodiment, the acid reactivity of inorganic particles in the dental filling material contained in the dental composition is suppressed as described above. Therefore, even when used in a dental composition containing acidic components, the long-term shelf life of the dental composition can be improved.

[0035] The dental composition of this embodiment is not particularly limited, but for example, it is a dental composition containing an acidic group-containing polymerizable monomer. Examples of acidic group-containing polymerizable monomers include (meth)acrylates having an acidic group.

[0036] The (meth)acrylate monomer having acidic groups contained in the dental adhesive composition is not particularly limited, but examples include (meth)acrylate monomers having acidic groups such as phosphate groups, pyrophosphate groups, thiophosphate groups, carboxylic acid groups, sulfonic acid groups, and phosphonic acid groups. Note that the (meth)acrylate having acidic groups may have multiple acidic groups.

[0037] Examples of (meth)acrylates having a phosphate group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, 2-(meth)acryloyloxyethyl phenylhydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl phenylhydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 1,3-di(meth)acryloylpropane-2-dihydrogen phosphate, 1,3-di(meth)acryloylpropane-2-phenylhydrogen phosphate, and bis[5-{2-(meth)acryloyloxyethoxycarbonyl}heptyl]hydrogen phosphate.

[0038] Examples of (meth)acrylates having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, and bis[10-(meth)acryloyloxydecyl] pyrophosphate.

[0039] Examples of (meth)acrylates having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate, 9-(meth)acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, and 11-(meth)acryloyloxyundicyl Examples include 12-(meth)acryloyloxide decyl dihydrogenthiophosphate, 13-(meth)acryloyloxytridecyl dihydrogenthiophosphate, 14-(meth)acryloyloxytetradecyl dihydrogenthiophosphate, 15-(meth)acryloyloxypentadecyl dihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogenthiophosphate, 17-(meth)acryloyloxyheptadecyl dihydrogenthiophosphate, 18-(meth)acryloyloxyoctadecyl dihydrogenthiophosphate, 19-(meth)acryloyloxynonadecyl dihydrogenthiophosphate, and 20-(meth)acryloyloxyicosyl dihydrogenthiophosphate.

[0040] Examples of (meth)acrylates having a carboxylic acid group include 2-methacryloyloxyethyl succinic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 4-(meth)acryloyloxyethyl trimellitic anhydride, 4-(meth)acryloyloxydecyl trimellitic acid, 4-(meth)acryloyloxydecyl trimellitic anhydride, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di(meth)acryloyloxypyromellitic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxyethyl phthalic acid, and 2-(meth)acryloyloxyethyl hexahydrophthalic acid.

[0041] Examples of (meth)acrylates having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth)acrylate.

[0042] Examples of (meth)acrylates having a phosphonic acid group include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, and 10-(meth)acryloyloxydecyl-3-phosphonoacetate.

[0043] These (meth)acrylate monomers having acidic groups may be used individually or in combination of two or more.

[0044] Among the (meth)acrylates having acidic groups, those having phosphate groups, thiophosphate groups, or carboxylic acid groups are preferred in terms of the solubility of the smear layer on the tooth surface of the dental adhesive composition, demineralization of tooth structure, and especially adhesion to enamel.

[0045] Furthermore, among these, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), 10-methacryloyloxydecyl dihydrogen thiophosphate (MDTP), 4-methacryloyloxyethyl trimellitic anhydride (4-META), etc., are preferred in terms of improving the adhesiveness of dental adhesive compositions.

[0046] The content of (meth)acrylate monomers having acid groups in the dental adhesive composition is not particularly limited and can be, for example, 0.1% by mass or more and 30% by mass or less, preferably 1% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 25% by mass or less.

[0047] If the content of (meth)acrylate monomers having acid groups in the dental adhesive composition is 0.1% by mass or more, the adhesion of the dental adhesive composition to tooth structure is further improved. 30 When the concentration is below mass%, the curing properties of the dental adhesive composition are improved.

[0048] The dental adhesive composition of this embodiment may contain other components as long as they do not impair the objective of the present invention. Examples of other components included in the dental adhesive composition include (meth)acrylates that do not have acid groups, polymerization initiators, polymerization inhibitors, fillers, and solvents. Examples of polymerization initiators include chemical polymerization initiators and photopolymerization initiators.

[0049] The chemical polymerization initiator is not particularly limited, and for example, thiourea derivatives, vanadium compounds, tertiary amines, and organic peroxides can be used.

[0050] Thiourea derivatives function as reducing agents among chemical polymerization initiators.

[0051] The thiourea derivatives are not particularly limited and include, for example, ethylenethiourea, N-methylthiourea, N-ethylthiourea, N-propylthiourea, N-butylthiourea, N-laurylthiourea, N-phenylthiourea, N-cyclohexylthiourea, N,N-dimethylthiourea, N,N-diethylthiourea, N,N-dipropylthiourea, N,N-dibutylthiourea, N,N-dilaurylthiourea, N,N-diphenylthiourea, N,N-dicyclohexylthiourea, trimethylthiourea, tetramethylthiourea, N-acetylthiourea, N-benzoylthiourea, 1-allyl-3-(2-hydroxyethyl)-2-thiourea, 1-(2-tetrahydrofurfuryl)-2-thiourea, N-tert-butyl-N'-isopropylthiourea, 2-pyridylthiourea, and the like.

[0052] These thiourea derivatives may be used individually or in combination of two or more. Among these, N-benzoylthiourea is preferred in terms of improving the curability of dental adhesive compositions.

[0053] The content of thiourea derivative in the dental adhesive composition is not particularly limited, but is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less. When the content of thiourea derivative in the dental adhesive composition is 0.1% by mass or more, the curability of the dental adhesive composition is further improved, and when it is 5% by mass or less, the solubility of the thiourea derivative in the dental adhesive composition with respect to (meth)acrylate is improved.

[0054] Vanadium compounds function as reducing agents among chemical polymerization initiators.

[0055] The vanadium compound is not particularly limited and includes, for example, oxovanadium oxalate, vanadylacetylacetonate, vanadium acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, and two or more may be used in combination. Among these, vanadylacetylacetonate is preferred in terms of the curability of the dental adhesive composition.

[0056] The vanadium compound content in the dental adhesive composition is not particularly limited, but is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.0015% by mass or more and 1% by mass or less, and even more preferably 0.002% by mass or more and 0.1% by mass or less. When the vanadium compound content in the dental adhesive composition is 0.001% by mass or more, the curability of the dental adhesive composition is further improved, and when it is 5% by mass or less, the storage stability of the dental adhesive composition is further improved.

[0057] Tertiary amines function as reducing agents among chemical polymerization initiators.

[0058] Tertiary amines are not particularly limited and include, for example, tertiary aliphatic amines and tertiary aromatic amines.

[0059] Examples of tertiary aliphatic amines include N,N-dimethylaminoethyl methacrylate and triethanolamine.

[0060] Examples of tertiary aromatic amines include p-dialkylaminobenzoate alkyl, 7-dimethylamino-4-methylcoumarin, N,N-dimethylaniline, N,N-dibenzylaniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N,2,4,6-pentamethylaniline, N,N,2,4-tetramethylaniline, and N,N-diethyl-2,4,6-trimethylaniline.

[0061] Among these, tertiary amines are preferably tertiary aromatic amines, and more preferably alkyl p-dialkylaminobenzoates.

[0062] Examples of alkyl p-dialkylaminobenzoates include methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, propyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, and propyl p-diethylaminobenzoate.

[0063] These tertiary amines may be used individually or in combination of two or more.

[0064] Organic peroxides function as oxidizing agents among chemical polymerization initiators.

[0065] Examples of organic peroxides include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-di(hydroperoxy)hexane, p-diisopropylbenzene monohydroperoxide, p-methane hydroperoxide, and pinan hydroperoxide.

[0066] These organic peroxides may be used individually or in combination of two or more. Among these, cumene hydroperoxide is preferred in terms of the curing properties of the dental adhesive composition.

[0067] The content of organic peroxides in the dental adhesive composition is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and even more preferably 0.1% by mass or more and 3% by mass or less. When the content of organic peroxides in the dental adhesive composition is 0.01% by mass or more, the curing properties of the dental adhesive composition are further improved, and when it is 10% by mass or less, the working time of the dental adhesive composition is extended.

[0068] The photopolymerization initiator is not particularly limited and includes, for example, camphorquinone (CQ), ethyl 4-dimethylaminobenzoate (EPA), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzyl ketal, diacetyl ketal, benzyldimethyl ketal, benzyldiethyl ketal, benzylbis(2-methoxyethyl) ketal, 4,4'-dimethyl(benzyldimethyl ketal), anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethyl Examples include ruanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trifluoromethylthioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, bis(4-dimethylaminophenyl)ketone, and 4,4'-bis(diethylamino)benzophenone.

[0069] These photopolymerization initiators may be used individually or in combination of two or more. Among these, camphorquinone (CQ), ethyl 4-dimethylaminobenzoate (EPA), and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) are preferred for improving the curability of dental adhesive compositions.

[0070] The content of the photopolymerization initiator in the dental adhesive composition is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 8% by mass or less, and even more preferably 1% by mass or more and 5% by mass or less.0.01 When the amount is above mass%, the curing properties of the dental adhesive composition are further improved. 10 When the amount is below mass%, the storage stability of the dental adhesive composition is further improved.

[0071] Polymerization inhibitors include, for example, dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol) (BHT) and 6-tert-butyl-2,4-xylenol.

[0072] These polymerization inhibitors may be used individually or in combination of two or more. Among these, dibutylhydroxytoluene (BHT) is preferred in terms of improving the curability of dental adhesive compositions.

[0073] The content of polymerization inhibitors in dental adhesive compositions is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less. The content of photopolymerization initiators in dental adhesive compositions is 0.01 When the concentration is between 5% by mass and 5% by mass, the storage stability of the dental adhesive composition is improved.

[0074] The filler is not particularly limited, but examples include colloidal silica, fine silica particles with a hydrophobic surface treatment (hydrophobic fumed silica), aluminum oxide, fluoroaluminosilicate glass, and barium glass. Among these, hydrophobic fumed silica (e.g., Aerosil®) is preferred. These fillers may be used individually or in combination of two or more.

[0075] The amount of filler in the dental adhesive composition is preferably, for example, 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less.

[0076] If the amount of filler in the dental adhesive composition is 0.1% by mass or more, the viscosity of the dental adhesive composition increases, improving its handling properties. Furthermore, if the amount of filler in the dental adhesive composition is 30% by mass or less, the viscosity of the dental adhesive composition containing the glass does not become excessively high, maintaining high handling properties.

[0077] The solvent is not particularly limited, but examples include water and organic solvents.

[0078] Examples of organic solvents include ethanol, acetone, and propanol.

[0079] In this embodiment, even when a dental composition containing such an acidic group-containing polymerizable monomer is used, the acid reactivity of the inorganic particles in the dental filling material contained in the dental composition is suppressed as described above. Therefore, even when a dental filling material containing inorganic particles containing polyvalent metal elements is used in a dental composition containing an acidic component, the long-term storage properties of the dental composition can be improved.

[0080] Because the dental composition of this embodiment provides such effects, it can be preferably applied to self-adhesive dental cements, dental composite resins, ionomer cements containing polyacrylic acid, and the like. [Examples]

[0081] The present invention will be further described below with reference to examples. In the examples and comparative examples, barium glass was treated under the conditions shown in Table 1, and then each component was blended to prepare a one-component dental composite resin. Various tests and evaluations were performed according to the methods described below. In the following, "%" refers to mass percentage unless otherwise specified.

[0082] <Glass filler> As glass fillers, barium glass A and barium glass B were used. For barium glass A, a glass with 10% Al2O3, 10% B2O3, 25% BaO, and 55% SiO2 was used. For barium glass B, a glass with 10% Al2O3, 10% B2O3, 29% BaO, 49% SiO2, and 2% fluorine was used.

[0083] <EDTA treatment> To the glass, an EDTA aqueous solution (concentration 10 g / L) five to ten times the weight of the glass was added and stirred. The EDTA aqueous solution was removed by filtration, distilled water was added and stirred (washed), and then the distilled water was removed by filtration. The washed glass was dried in an 80°C thermostat and crushed in an automatic mortar. At this time, the particle size was confirmed.

[0084] After crushing, in an electric furnace 400℃ and Heat treatment was performed at 600°C. After the heat treatment, silane treatment was performed by dropping a silane coupling agent while stirring the glass in a mortar. The glass after silane treatment was heat-treated at 80°C and recovered.

[0085] <Acid treatment> To the glass, a hydrochloric acid aqueous solution five to ten times the weight of the glass was added and stirred. The acid aqueous solution was removed by filtration, distilled water was added and stirred (washed), and then the distilled water was removed by filtration. The washed glass was dried in an 80°C thermostat and crushed in an automatic mortar. At this time, the particle size was confirmed.

[0086] After crushing, in an electric furnace 200℃、400℃、 600°C and 800℃ Heat treatment was performed. After the heat treatment, silane treatment was performed by dropping a silane coupling agent while stirring the glass in a mortar. The glass after silane treatment was heat-treated at 80°C and recovered.

[0087] <Consistency test> Each paste was filled into a polypropylene syringe, defoamed by centrifugation, and a sample left standing for a predetermined number of days in a 23°C or 45°C thermostat was used as a sample for the consistency test. thisWeigh out 0.1g of the sample and place it in a constant temperature room at 23°C (50% humidity) and mound it up in the center of a polyester film (5cm x 5cm). Applicable The sample was left to stand.

[0088] Another polyester film (5cm x 5cm), a glass plate, and a weight were placed on top, and a total load of 860g was applied. After 10 seconds, the major and minor axes of the sample were measured, and the arithmetic mean of the two was calculated as the consistency (mm).

[0089] Note that the longest diameter of the sample is the longest diameter passing through the center of the sample. Meaning The minor axis of a sample refers to the diameter passing through the center of the sample that is perpendicular to the major axis of the sample.

[0090] Dental composite resin paste stored at 45°C should be removed from the incubator before measurement. 2 In a constant temperature room at 3°C ​​(50% humidity) 1 hour The consistency was measured after the mixture had been allowed to stand.

[0091] Initial consistency was measured the day after syringe filling. The change in consistency (XY) was defined as the change in consistency between the initial consistency (X) and the consistency after storage (Y). Evaluations A and B indicated good storage stability, while evaluation C indicated poor storage stability. The results are shown in Table 1.

[0092] <Storage stability at room temperature> A: Even after storage for more than one year, the change in consistency is less than 10 mm. B: Consistency change of 10mm or more after storage for 6 months to 1 year. C: Consistency change of 10 mm or more within 6 months

[0093] <Storage stability at 45°C for 4 weeks> A: Consistency change is less than 5 mm B: Consistency change of 5 mm or more but less than 10 mm C: Consistency change of 10 mm or more

[0094] Examples and comparative examples are described below.

[0095] [Example 1] As a glass filler, 60% barium glass A was treated with EDTA-2Na solution and then heat-treated at 600°C. 10% 10-methacryloyloxydecyl dihydrogen phosphate (MDP) was used as the acidic group-containing polymerizable monomer (acid polymerizable monomer), 20% di-2-methacryloyloxyethyl 2,2,4-trimethylhexamethylenedicarbamate (UDMA) and 7% triethylene glycol dimethacrylate (TEGDMA) were used as other polymerizable monomers, 1% camphorquinone and 1.9% p-dimethylaminobenzoate ethyl (EPA) were used as polymerization initiators, and 0.1% dibutylhydroxytoluene was used as a polymerization inhibitor. The conditions and results of Example 1 are shown in Table 1.

[0096] [Example 2] As an alternative to other polymerizable monomers, TEGDMA 7% Glycerin dimethacrylate The preparation was carried out in the same manner as in Example 1, except that 7% (GDMA) was used. The conditions and results of Example 2 are shown in Table 1.

[0097] [Example 3] The preparation was carried out in the same manner as in Example 1, except that 7% bisphenol A diglycidyl methacrylate (Bis-GMA) was used instead of 7% TEGDMA as the other polymerizable monomer. The conditions and results of Example 3 are shown in Table 1.

[0098] [Example 4] Example 4 was prepared in the same manner as in Example 3, except that 60% barium glass A was treated with EDTA-2Na solution and no heat treatment was performed. The conditions and results of Example 4 are shown in Table 1.

[0099] [Example 5] The preparation was the same as in Example 3, except that the solution was treated with EDTA-3Na instead of EDTA-2Na and no heat treatment was performed. The conditions and results of Example 5 are shown in Table 1.

[0100] [Example 6] The preparation was the same as in Example 3, except that the solution was treated with EDTA-4Na instead of EDTA-2Na and no heat treatment was performed. The conditions and results for Example 6 are shown in Table 1.

[0101] [Example 7] Except for setting the heat treatment temperature to 400°C, the procedure was the same as in Example 1. Made The conditions and results for Example 7 are shown in Table 1.

[0102] [Example 8] The preparation was the same as in Example 1, except that treatment was performed with EDTA-3Na solution instead of EDTA-2Na solution. Made The conditions and results for Example 8 are shown in Table 1.

[0103] [Example 9] The preparation was the same as in Example 1, except that the treatment was done with EDTA-4Na solution instead of EDTA-2Na solution. Made The conditions and results for Example 9 are shown in Table 1.

[0104] [Example 10] Except for using barium glass B instead of barium glass A, the preparation was the same as in Example 7. Made The conditions and results for Example 10 are shown in Table 1.

[0105] [Example 11] Except for using barium glass B instead of barium glass A, the preparation was the same as in Example 1. Made The conditions and results for Example 11 are shown in Table 1.

[0106] [Example 12] The preparation was the same as in Example 11, except that treatment was performed with EDTA-3Na solution instead of EDTA-2Na solution. Made The conditions and results for Example 12 are shown in Table 1.

[0107] [Example 13] The preparation was the same as in Example 11, except that treatment was performed with EDTA-4Na solution instead of EDTA-2Na solution. Made The conditions and results for Example 13 are shown in Table 1.

[0108] [Comparative Example 1] The preparation was carried out in the same manner as in Example 1, except that neither treatment with EDTA solution nor heat treatment was performed. The conditions and results of Comparative Example 1 are shown in Table 1.

[0109] [Comparative Example 2] The preparation was the same as in Example 1, except that it was heat-treated at 200°C without treatment with EDTA solution. The conditions and results for Comparative Example 2 are shown in Table 1.

[0110] [Comparative Example 3] The preparation was the same as in Example 1, except that it was heat-treated at 400°C without treatment with EDTA solution. The conditions and results of Comparative Example 3 are shown in Table 1.

[0111] [Comparative Example 4] The preparation was the same as in Example 1, except that it was heat-treated at 600°C without treatment with EDTA solution. The conditions and results of Comparative Example 4 are shown in Table 1.

[0112] [Comparative Example 5] Without treatment with EDTA solution, 800 The preparation was the same as in Example 1, except that it was heat-treated at °C. The conditions and results for Comparative Example 5 are shown in Table 1.

[0113] [Table 1]

[0114] Table 1 shows that Examples 1-13, which were treated with EDTA solution, showed a consistency change of less than 10 mm at both room temperature and 45°C for 4 weeks, indicating good storage stability. In contrast, Comparative Examples 1-5, which were not treated with EDTA solution, showed a consistency change of 10 mm or more at both room temperature and 45°C for 4 weeks, indicating poor storage stability.

[0115] Furthermore, when glass was treated with hydrochloric acid (acid treatment), no corrosion of the equipment used was observed in Examples 1 to 13, whereas corrosion of the equipment used was observed in Comparative Examples 1 to 5.

[0116] These results show that treating inorganic particles containing polyvalent metal elements with a solution containing a chelating agent suppresses equipment deterioration and improves the long-term shelf life of dental filling materials containing these treated inorganic particles, even when used in dental compositions containing acidic components.

[0117] Although embodiments of the present invention have been described above, the present invention is not limited to any particular embodiment, and various modifications and changes are possible within the scope of the invention as described in the claims.

Claims

1. A method for manufacturing a dental filling material containing inorganic particles containing polyvalent metal elements, The process includes treating the inorganic particles with a solution containing an aminopolycarboxylate salt, which is a chelating agent that does not form an acid, followed by a silane treatment. A method for manufacturing dental filling materials.

2. The aminopolycarboxylate salt is ethylenediaminetetraacetate. A method for manufacturing a dental filling material according to claim 1.

3. Furthermore, a method for producing a dental filling material according to claim 1 or 2, comprising a heat treatment step.

4. A dental composition containing a dental filling material manufactured by the method described in any one of claims 1 to 3.

5. Contains an acidic group-containing polymerizable monomer, The dental composition according to claim 4.

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