Dental composite resin kit

Abstract

To provide a dental composite resin kit in which the number of dental composite resins to be used together is relatively small and a wide range of color tones can be reproduced when aesthetic filling restoration is performed to teeth of various color tones.SOLUTION: The first and second dental composite resins have a difference in contrast ratio of 0.3 or less, each of the contrast ratios of 0.3 to 0.75, and a color difference Δ E of 2 or more, when the contrast ratios of the cured bodies at the 1mm of the thickness are measured.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dental composite resin kit. [Background technology]

[0002] Dental composite resins are used in the dental field.

[0003] Patent Document 1 proposes a dental filling and restorative kit that combines an enamel restorative material and a dentin restorative material. Patent Document 2 proposes a dental filling and restorative kit that combines an external filler and a dental polymerizable composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2014 / 148293 [Patent Document 2] Published Patent Application No. 2016-175851 Summary of the Invention [Problem to be solved by the invention]

[0005] These conventional kits require the stocking of numerous composite resins in various shades in order to perform aesthetic filling restorations on teeth of various shades. Furthermore, because the kits are designed to use a variety of composite resins and materials in combination, there is room for reducing the burden on dental clinicians. For example, commercially available kits offer a lineup of numerous shades, such as enamel shades (for upper layer fillings) and body shades (for lower layer fillings), each designed to achieve a color similar to that of natural teeth by filling the areas of the cavity that correspond to the dentin and enamel.

[0006] The present invention provides a dental composite resin kit that allows aesthetic filling and restoration of teeth by switching the corresponding parts from the upper layer to the lower layer and / or from the lower layer to the upper layer depending on the color tone of the tooth to be filled, without limiting the corresponding parts of the two laminated dental composite resins to the lower or upper layer in advance.Therefore, by switching the corresponding parts from the upper layer to the lower layer and / or from the lower layer to the upper layer, it is possible to reproduce more color tones than conventional kits with the same number of composite resins as conventional kits, and to perform aesthetic filling and restoration of teeth of various color tones. [Means for solving the problem]

[0007] In order to solve the above problems, the inventors have conducted extensive research into laminating two dental composite resins of different shades, and have found that when performing aesthetic filling and restoration on a tooth, two dental composite resins that satisfy a specific relationship in terms of shade can be used to perform aesthetic filling and restoration on a tooth that has different shades both before and after swapping the lower and upper layers, and that by including two dental composite resins that satisfy this specific relationship in a kit, it is possible to reproduce a wide range of shades and perform aesthetic filling and restoration on teeth of various shades, even if the number of dental composite resins used together is reduced. The present invention is based on the above findings.

[0008] The present invention provides a kit containing at least a first dental composite resin and a second dental composite resin, wherein when the contrast ratios of the first dental composite resin and the second dental composite resin are measured for a 1 mm thick cured body, the difference in contrast ratio is within 0.3, and the respective contrast ratios are 0.3 to 0.75, and the L of the 1 mm thick cured body of the first dental composite resin is * a * b * The color tone in the space is measured against a white background (L1 * , a1 * , b1 * ) and the L of the hardened body of the second dental composite resin with a thickness of 1 mm * a* b * The color tone in the space is measured against a white background (L2 * , a2 * , b2 * ) the color difference ΔE represented by the following formula (1) is 2 or more. Equation (1): ΔE = {(L1 * -L2 * ) 2 +(a1 * -a2 * ) 2 +(b1 * -b2 * ) 2} 1 / 2

[0009] In the present invention, the first dental composite resin and the second dental composite resin are Regarding a laminate consisting of a 0.3mm thick hardened dental composite resin and a 0.7mm thick hardened dental composite resin, The hardened dental composite resin with a thickness of 0.3 mm is placed on the front side. * a * b * The color tone in the space is measured against a white background (L S1 * , a S1 * , b S1 * )year, The hardened dental composite resin with a thickness of 0.7 mm is placed on the front side. * a * b * The color tone in the space is measured against a white background (L S2 * , a S2 * , b S2 * ), The brightness difference ΔL is expressed by the following formula (2): * 1 and the saturation difference ΔC expressed by the following formula (3) *1 may satisfy the relationship of the following formula (4). Formula (2): ΔL * 1=|L S1 * -L S2 * | Equation (3):ΔC * 1=|{(a S1 * ) 2 +(b S1 * ) 2} 1 / 2 -{(a S2 * ) 2 +(b S2 * ) 2} 1 / 2 | Equation (4): ΔL * 1<ΔC * 1

[0010] In the present invention, at least one of the first dental composite resin and the second dental composite resin may have a light diffusion index of 1 or more in a cured form when the thickness is 1 mm.

[0011] In the present invention, the first dental composite resin and the second dental composite resin are Regarding the laminate of the other dental composite resin hardened body with a thickness of 0.3 mm and the other dental composite resin hardened body with a thickness of 0.7 mm, The hardened dental composite resin with a thickness of 0.3 mm is placed on the front side. * a * b * The color tone in the space is measured against a white background (L S3 * , a S3 * , b S3 * )year, The hardened dental composite resin with a thickness of 0.7 mm is placed on the front side. * a* b * The color tone in the space is measured against a white background (L S4 * , a S4 * , b S4 * ), The brightness difference ΔL is expressed by the following formula (5): * 2 and the saturation difference ΔC expressed by the following formula (6) * 2 can satisfy the relationship of the following formula (7). Equation (5): ΔL * 2=|L S3 * -L S4 * | Equation (6):ΔC * 2=|{(a S3 * ) 2 +(b S3 * ) 2} 1 / 2 -{(a S4 * ) 2 +(b S4 * ) 2} 1 / 2 | Equation (7): ΔL * 2<ΔC * 2 [Effects of the Invention]

[0012] The dental composite resin kit of the present invention can reproduce a wide range of colors and perform aesthetic filling and restoration on teeth of various colors, even when using a small number of dental composite resins in combination, thereby reducing the burden on the surgeon. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention also provides a dental composite resin kit that allows the color tone of the dental composite resin to be filled on the surface (labial side or occlusal side) and cavity bottom (lingual side or pulp side) of the restoration site to be selected / switched as desired when filling the dental composite resin in layers.

[0014] The present invention also provides a dental composite resin kit that includes multiple colors of dental composite resin that are tinted to a translucent to slightly opaque color similar to that of natural teeth, and that allows the user to choose between single-color and / or two-color layered filling when filling the dental composite resin into the restoration area.

[0015] In the present invention, the first dental composite resin and the second dental composite resin are laminated with a 0.3 mm thick hardened body of one dental composite resin and a 0.7 mm thick hardened body of the other dental composite resin, and the hardened body of the 0.3 mm thick dental composite resin is placed on the front side. * a * b * The color tone in the space is measured against a white background (L S1 * , a S1 * , b S1 * ) and a hardened dental composite resin with a thickness of 0.7 mm was placed on the front side. * a * b * The color tone in the space is measured against a white background (L S2 * , a S2 * , b S2 * ), the brightness difference ΔL expressed by the following formula (2) * 1 and the saturation difference ΔC expressed by the following formula (3) * 1 can satisfy the relationship of the following formula (4). By satisfying this relationship, when the upper and lower layers of the composite resin to be layered during restoration are switched, the saturation can be changed while suppressing the change in lightness, making it easier for the surgeon to predict color compatibility and enabling control of saturation. Formula (2): ΔL * 1=|L S1 * -L S2 * | Equation (3):ΔC * 1=|{(a S1 * ) 2 +(b S1 * ) 2} 1 / 2 -{(a S2 * ) 2 +(b S2 * ) 2} 1 / 2 | Equation (4): ΔL * 1<ΔC * 1

[0016] In this case, the first dental composite resin and the second dental composite resin are laminated with a 0.3 mm thick hardened body of the other dental composite resin and a 0.7 mm thick hardened body of one dental composite resin, with the 0.3 mm thick hardened body of the dental composite resin on the front side. * a * b * The color tone in the space is measured against a white background (L S3 * , a S3 * , b S3 * ) and a hardened dental composite resin with a thickness of 0.7 mm was placed on the front side. * a * b * The color tone in the space is measured against a white background (L S4 * , a S4 * , b S4 * ), the brightness difference ΔL expressed by the following formula (5) * 2 and the saturation difference ΔC expressed by the following formula (6) *2 can satisfy the relationship of the following formula (7). Equation (5): ΔL * 2=|L S3 * -L S4 * | Equation (6):ΔC * 2=|{(a S3 * ) 2 +(b S3 * ) 2} 1 / 2 -{(a S4 * ) 2 +(b S4 * ) 2} 1 / 2 | Equation (7): ΔL * 2<ΔC * 2

[0017] In the present invention, at least one of the first dental composite resin and the second dental composite resin may have a light diffusion index of 1 or more in a cured form when the thickness is 1 mm.

[0018] In the present invention, the first dental composite resin and the second dental composite resin can each contain (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) a filler and a colorant.

[0019] The dental composite resin kit of the present invention is described in detail below. The dental composite resin kit of the present invention is used as a dental adhesive, a dental abutment construction material, a dental resin cement, a dental coating material, a dental pit and fissure sealant, a dental manicure material, a dental adhesive material for fixing loose teeth, a dental hard resin, a dental cutting material, a dental 3D printer material, etc.

[0020] In clinical dentistry, various treatments are performed to restore aesthetic and functional appearance to tooth defects caused by caries, fractures, etc., using direct methods, such as restoration with dental adhesives and composite resins, and indirect methods, such as restoration with prosthetic devices made of ceramics or dental hard resins using dental resin cement. In addition, dental adhesives are used to bond dental composite resins to various dental materials and natural teeth, dental adhesives for fixing loose teeth, dental coating materials to protect sensitive and formed vital teeth from external irritation and secondary caries, dental pit and fissure sealants to prevent caries by filling deep fissures in molars, dental nail polish to temporarily restore aesthetics by masking tooth discoloration, and dental core buildup materials to form abutment teeth when the crown of a tooth has collapsed due to caries. In recent years, new composite materials have been developed, such as dental cutting materials for creating prosthetic devices using CAD / CAM processing and dental 3D printing materials for creating prosthetic devices using 3D printers, and a variety of dental materials are used in treatment. These materials are prepared into a uniform paste by mixing a resin matrix consisting of several types of polymerizable monomers, various fillers such as inorganic fillers and organic-inorganic composite fillers, and a polymerization initiator, depending on the application. To cite some examples, dental filling composite resins are filled into teeth in an uncured paste state, and then shaped to the anatomical shape of natural teeth using dental instruments and other dental tools. They are then cured by exposure to light using a dental light curing device or similar device. The light emitted from the light curing device generally has a wavelength range of approximately 360 to 500 nm and an intensity of 100 to 2000 mW / cm. 2 On the other hand, dental resin cement is used to bond a prosthetic device to a cavity or an abutment tooth, and is hardened by irradiating it with light after the prosthetic device is attached to the cavity or the abutment tooth.

[0021] The photopolymerization initiators used in these dental materials are widely composed of photosensitizers or a combination of a photosensitizer and an appropriate photopolymerization accelerator. Acylphosphine oxide compounds and α-diketone compounds are known as photosensitizers, and α-diketone compounds in particular have the ability to initiate polymerization in the visible light wavelength range, which has little effect on the human body. Furthermore, photoacid generators and tertiary amine compounds are well-known compounds to be combined with photosensitizers.

[0022] On the other hand, dental composite resins need to be adapted to various shapes to fit the complex shapes of teeth.Furthermore, matching the color of dental composite resins with the tooth to create aesthetic restorations contributes to improving patients' quality of life.

[0023] However, tooth colors vary from patient to patient, and for dentists, having to stock a large number of composite resins in different colors and using materials whose color is designed to be used in combination with multiple composite resins and materials is a burden, and there was room for improvement.

[0024] [(A) Polymerizable Monomer] In the present invention, the polymerizable monomer (A) contained in the dental composite resin can be any known polymerizable monomer. In the polymerizable monomer or compound having a polymerizable group in the present invention, the polymerizable group preferably exhibits radical polymerization. Specifically, from the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In this specification, "(meth)acrylic" refers to acrylic and / or methacrylic, "(meth)acryloyl" refers to acryloyl and / or methacryloyl, "(meth)acrylate" refers to acrylate and / or methacrylate, and "(meth)acrylamide" refers to acrylamide and / or methacrylamide. Polymerizable monomers having a substituent at the α-position of the acrylic group and / or acrylamide group are also preferred. Examples include those having one radically polymerizable group, those having two radically polymerizable groups, those having three or more radically polymerizable groups, those having an acidic group, an alkoxysilyl group, and those having a sulfur atom.

[0025] Specific examples of polymerizable monomers having one radically polymerizable group and no acidic group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-methylol (meth)acrylamide, N -hydroxyethyl (meth)acrylamide, N,N-(dihydroxyethyl) (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acrylamide.

[0026] Specific examples of polymerizable monomers having two radical polymerizable groups and no acidic group include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2-(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, 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 di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,Examples include 4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA") and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane.

[0027] Specific examples of polymerizable monomers having three or more radically polymerizable groups and no acidic group include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0028] The polymerizable monomer having an acidic group can be used without limitation as long as it has one or more polymerizable groups and at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a sulfonic acid group, a carboxylic acid group, etc. By including a polymerizable monomer having an acidic group, it is possible to impart adhesiveness to tooth structures and prosthetic devices.

[0029] Specific examples of the polymerizable monomer having a phosphoric acid group 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)acryloyloxyhexyl dihydrogen phosphate, 9-(meth)acryloyloxyheptyl dihydrogen phosphate, 10-(meth)acryloyloxyhexyl dihydrogen phosphate, 11-(meth)acryloyloxyhexyl dihydrogen phosphate, 12-(meth)acryloyloxyhexyl dihydrogen phosphate, 13-(meth)acryloyloxyhexyl dihydrogen phosphate, 14-(meth)acryloyloxyhexyl dihydrogen phosphate, 15-(meth)acryloyloxyhexyl dihydrogen phosphate, 16-(meth)acryloyloxyhexyl dihydrogen phosphate, 17-(meth)acryloyloxyheptyl dihydrogen phosphate, 18-(meth)acryloyloxyhexyl dihydrogen phosphate, 19-(meth)acryloyloxyhexyl dihydrogen phosphate, 20-(meth)acryloyloxyhexyl dihydrogen phosphate, 21-(meth)acryloyloxyhexyl dihydrogen phosphate, 22-(meth)acryloyloxyhexyl dihydrogen phosphate, 23-(meth)acryloyloxyhexyl dihydrogen phosphate, 24-(meth)acryloyloxyhexyl dihydrogen phosphate, 25-(meth)acryloyloxyhexyl dihydrogen phosphate, 26-(meth)acryloyloxyhexyl dihydrogen phosphate, 27- Acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate phosphate, bis[2-(meth)acryloyloxyethyl]hydrogenphosphate, bis[4-(meth)acryloyloxybutyl]hydrogenphosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-(meth)acryloyloxynonyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3-di( Examples thereof include 2-(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogen phosphate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0030] Specific examples of polymerizable monomers 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, bis[10-(meth)acryloyloxydecyl] pyrophosphate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0031] Specific examples of polymerizable monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, and 9-(meth)acryloyloxy. Examples of suitable thiophosphates include 1-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, and 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate; their acid chlorides, alkali metal salts, and ammonium salts; and (meth)acrylamide compounds in which the ester bond in these compounds is replaced with an amide bond. Polymerizable monomers having a thiophosphate group are also classified as polymerizable monomers having a sulfur atom.

[0032] Specific examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0033] Specific examples of polymerizable monomers having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl(meth)acrylate.

[0034] Polymerizable monomers having a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule and (meth)acrylic compounds having multiple carboxyl groups in the molecule. Specific examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, and 4-(meth)acryloyloxybenzoic acid. Examples of the acryloyloxybenzoic acid include 2-(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)acryloyloxyethyl hydrogen phthalate, and 2-(meth)acryloyloxyethyl hydrogen maleate; acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.Specific examples of the (meth)acrylic compound having multiple 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)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4 ...4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth Examples thereof include acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; acid anhydrides and acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0035] Preferred examples include 10-methacryloyloxydecyl dihydrogen phosphate and 6-methacryloxyhexyl phosphonoacetate. The amount of polymerizable monomer having an acidic group is 1 part by mass or more, more preferably 1 part by mass or more and 30 parts by mass or less, per 100 parts by mass of polymerizable monomers contained in the dental composite resin, from the viewpoint of imparting adhesiveness. If the amount is less than 1 part by mass, sufficient adhesiveness to tooth structure, metal, and metal oxides may not be exhibited, and if the amount is 30 parts by mass or more, storage stability may be reduced.

[0036] Specific examples of polymerizable monomers having an alkoxysilyl group include (meth)acrylic compounds and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and (meth)acrylic compounds and (meth)acrylamide compounds having multiple alkoxysilyl groups in the molecule. Examples of the silane include 2-(meth)acryloxyethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, and 11-(meth)acryloxyundecyltrimethoxysilane.Furthermore, examples of compounds having a urethane group or an ether group include 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontan-40-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-silanonadecan-19-oyl)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, and 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate. acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl(meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl(meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl(meth)acrylate 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-silanonadecan-19-yl)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-yl(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-yl(meth)acrylate 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silahexacosan-26-yl (meth)acrylate, 4,4-diethoxy-13-oxo-3,12,17-trioxa-14-aza-4-silanonadecan-19-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaicosan-20-yl (meth)acrylate, 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyl di(meth)acrylate.

[0037] In the present invention, the dental composite resin may contain a sulfur-containing polymerizable monomer (A) to impart adhesion to precious metals. Known compounds containing one or more sulfur atoms and a polymerizable group can be used without limitation. Specifically, this refers to compounds having partial structures such as -SH, -SS-, >C=S, >CSC<, and >P=S, or compounds resulting from tautomerization. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate.

[0038] In addition to these polymerizable monomers, oligomers or prepolymers having at least one polymerizable group in the molecule may be used without any limitation. Furthermore, there is no problem even if the same molecule has a substituent such as a fluoro group. The above-described polymerizable monomers may be used alone or in combination.

[0039] In the present invention, the dental composite resin may contain a silane coupling agent as a polymerizable monomer (A) to impart adhesion to glass ceramics. While any known silane coupling agent can be used without limitation, 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane, etc. are preferred. From the perspective of imparting adhesion, the amount of the silane coupling agent is at least 1 part by mass, more preferably at least 5 parts by mass but less than 20 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers in the composition. Because the silane coupling agent as a polymerizable monomer is intended to impart adhesion to glass ceramics or resin materials containing a filler made of glass ceramics, it is blended separately from the surface treatment agent for the filler.

[0040] In the present invention, the dental composite resin may contain a polymerizable monomer having a sulfur atom as a polymerizable monomer (A) to impart adhesiveness to precious metals. From the viewpoint of imparting adhesiveness, the blending amount of the polymerizable monomer having a sulfur atom is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more but less than 20 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers contained in the dental composite resin.

[0041] <Photopolymerization initiator> In the present invention, the dental composite resin contains (B) a photosensitizer and (D) a photopolymerization accelerator as photopolymerization initiators, and may also contain (C) a photoacid generator, which are not particularly limited, and commonly used known compounds can be used without any restrictions.

[0042] [(B) Photosensitizer] Specific examples of the photosensitizer (B) that can be used in the present invention include α-diketones such as benzil, camphorquinone, camphorquinonecarboxylic acid, camphorquinonesulfonic acid, α-naphthyl, acetonaphthene, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and naphthoquinone; benzoins such as benzoin methyl ether and benzoin ethyl ether; Alkyl ethers, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone, benzophenones such as benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl) Phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl Bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxy 2,6-Dimethoxybenzoylbenzyl phosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropyl phosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethyl phosphine oxide, 2,6-dimethoxybenzoylbenzyl butyl phosphine oxide, 2,6-dimethoxybenzoylbenzyl octyl phosphine oxide, bis(2,4,6-trimethylbenzoyl) isobutyl phosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl acylphosphine oxides such as n-butylphosphine oxide, acylgermanium compounds such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-2, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-3, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-4, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-5, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-6, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-7, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-8, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-9, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-1 ...1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-2, 2-benzyl α-aminoacetophenones such as α-propanone-1; ketals such as benzil dimethyl ketal, benzil diethyl ketal, and benzil (2-methoxyethyl ketal); and titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl)-titanium, and bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium.

[0043] (B) The photosensitizer can be appropriately selected depending on the wavelength, intensity, and irradiation time of the light used for polymerization, as well as the types and amounts of other components to be combined. The photosensitizers can be used alone or in combination of two or more. Among these, α-diketone compounds having a maximum absorption wavelength in the visible light region are preferably used, and camphorquinone compounds such as camphorquinone, camphorquinonecarboxylic acid, and camphorquinonesulfonic acid are more preferred. Camphorquinone is particularly preferred because of its easy availability.

[0044] The amount of (B) photosensitizer blended is usually preferably 0.02 to 1 part by mass, more preferably 0.02 to 0.5 parts by mass, and even more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the total amount of (A) polymerizable monomer contained in the dental composite resin. If the amount of (B) photosensitizer blended is less than 0.02 parts by mass, the polymerization activity in response to irradiated light may be poor, resulting in insufficient curing. If the amount blended is more than 1 part by mass, sufficient curing properties are exhibited, but stability to ambient light decreases and yellowing increases. The dental hardenable composition of the present invention may contain only an α-diketone compound as the photosensitizer (B).

[0045] [(C) Photoacid generator] In the present invention, known compounds can be used without limitation as the photoacid generator (C) that can be used in the dental composite resin. Specific examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonic acid ester compounds. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. Iodonium salt compounds are more preferred. Iodonium salt compounds are easily sensitized by photosensitizers that absorb light in the visible light region.

[0046] Specific 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, and 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 s(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-dimethoxyphenyl)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)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,Examples include 6-bis(trichloromethyl)-s-triazine and 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine. Of these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

[0047] Any known iodonium salt compound can be used. To give a specific example, the structural formula of an iodonium salt compound can be represented by the following formula (8): [Formula (8)] [(R1)2I] + [A] - (In the formula [(R1)2I] + is the cationic moiety, [A] - is an anion moiety, and R1 in formula (8) represents an organic group bonded to I, and R1 may be the same or different. R1 represents, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, which may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogen.

[0048] Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl group, and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0049] Examples of heterocyclic groups having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Specific examples include monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, and fused polycyclic heterocyclic groups such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0050] Specific examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0051] Specific examples of alkenyl groups having 2 to 30 carbon atoms include straight-chain or branched ones such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl.

[0052] Furthermore, specific examples of the alkynyl group having 2 to 30 carbon atoms include straight-chain or branched ones such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, and 1-methyl-2-propynyl.

[0053] The above-mentioned aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms may have at least one substituent, and specific examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, and octadecyl; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, and tert-butyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy groups; linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, and octadecyl. Straight-chain or branched alkylcarbonyl groups having 2 to 18 carbon atoms, such as octanoyl; arylcarbonyl groups having 7 to 11 carbon atoms, such as benzoyl and naphthoyl; straight-chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl; phenoxycarbonyl aryloxycarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; linear or branched acyloxy groups having 2 to 19 carbon atoms, such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy;Arylthio groups having 6 to 20 carbon atoms, such as phenylthio, biphenylylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4-(methylthiobenzoyl)phenylthio, and 4-(ptert-butylbenzoyl)phenylthio; straight-chain or branched alkylthio groups having 1 to 18 carbon atoms, such as methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, and dodecylthio; phenylthio aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, dimethylphenyl, and naphthyl; heterocyclic groups having 4 to 20 carbon atoms, such as thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, and dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl; arylsulfinyl groups having 6 to 10 carbon atoms, such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl; Examples include arylsulfonyl groups having 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl), and naphthylsulfonyl; alkyleneoxy groups; cyano groups; nitro groups; and halogens such as fluorine, chlorine, bromine, and iodine.

[0054] Among iodonium salt compounds, aryliodonium salts are preferred because of their high stability. Furthermore, the aryl group preferably has a substituent to improve liposolubility. Specifically, linear alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl, and tridecyl, branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl, and functional groups in which one or more H atoms in these groups are replaced with F, perfluoroalkyl groups, and halogens are preferred as the substituent.

[0055] The structure of the anion moiety of the iodonium salt compound is not particularly limited, but examples include those containing atoms such as halogen, P, S, B, Al, and Ga. From a safety perspective, anions containing As or Sb can be used, but are not preferred for dental applications. Furthermore, the anion preferably contains an organic group such as an alkyl group, an alkoxy group, and / or an aryl group, and most preferably an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which at least one H is substituted with F. Iodonium salt compounds containing such an anion have high solubility in dental composite resins, preventing precipitation during low-temperature storage or long-term storage. They also dissolve in the composition quickly, thereby shortening production times. Furthermore, iodonium salt compounds containing an anion containing an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which at least one H is substituted with F are expected to have even higher solubility. Precipitation of the photoacid generator is undesirable because it can cause a decrease in photocolor stability and bending strength. The anion having an organic group such as an alkyl group, an alkoxy group, and / or an aryl group, in which at least one H may be substituted with F, may be an anion having any atom, but from the viewpoints of versatility and safety, an anion having P, S, B, Al, or Ga is preferred.

[0056] Examples of anions having no alkyl group and / or alkoxy group and / or aryl group include halogens such as chloride and bromide, perhalogen acids such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, camphorsulfonic acid, nitrate, acetate, chloroacetate, carboxylate, phenolate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, etc. Among these, p-toluenesulfonate, camphorsulfonic acid, and carboxylate are preferably used.

[0057] [A] of the iodonium salt compound of formula (8) - The anion moiety of the iodonium salt compound of formula (8) is preferably an anion having an organic group such as an alkyl group, an alkoxy group, and / or an aryl group, in which at least one H is substituted with F, because this improves the solubility in dental composite resins. Specifically, [A] of the iodonium salt compound of formula (8) - The alkyl group in the anion moiety preferably has 1 to 8 carbon atoms, and more preferably 1 to 4. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 4 or more, and preferably the ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 9 or more. It is more preferable that all hydrogen atoms in the hydrocarbon are substituted with fluorine. The dental composite resin may contain an iodonium salt composed of an anion having an alkyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0058] Specific examples of the alkyl group include straight-chain or branched perfluoroalkyl groups such as CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C.

[0059] [A] of the iodonium salt compound of formula (8) - The alkoxy group in the anion moiety preferably has 1 to 8 carbon atoms, and more preferably 1 to 4. Specific examples include linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and octoxy, and branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, and tert-butoxy. The ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 4 or more, and preferably the ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 9 or more. It is more preferable that all hydrogen atoms in the hydrocarbon are substituted with fluorine. The dental composite resin may contain an iodonium salt consisting of an anion having an alkoxy group with a different ratio of hydrogen atoms to fluorine atoms.

[0060] Furthermore, specific examples of the alkoxy group include linear or branched perfluoroalkoxy groups such as CF3O, CF3CF2O, CF3CF2CF2O, (CF3)2CFO, CF3CF2CF2CF2O, (CF3)2CFCF2O, CF3CF2(CF3)CFO, CF3CF2CF2CF2CF2O, CF3CF2CF2CF2CF2CF2CF2CF2CF2CF2O.

[0061] [A] of the iodonium salt compound of formula (8) -The phenyl group in the anion moiety has at least one hydrogen atom substituted with a fluorine atom and / or an alkyl group and / or an alkoxy group substituted with a fluorine atom. The alkyl group and / or alkoxy group substituted with a fluorine atom are preferably those described above. Particularly preferred examples of the phenyl group include perfluorophenyl groups such as pentafluorophenyl (CF), trifluorophenyl (CH), tetrafluorophenyl (CF), trifluoromethylphenyl (CF), bis(trifluoromethyl)phenyl ((CF)C), pentafluoroethylphenyl (CF), bis(pentafluoroethyl)phenyl ((CF)C), trifluoromethylfluorophenyl (CF), bistrifluoromethylfluorophenyl ((CF)C), pentafluoroethylfluorophenyl (CF), and bispentafluoroethylfluorophenyl ((CF)C). The dental composite resin may contain an iodonium salt consisting of an anion having a phenyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0062] [A] of the iodonium salt compound of formula (8) - A specific example of the anion portion of the anion having P is [(CF3CF2)3PF3] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [((CF3)2CF)4PF2] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - Anions containing S include [(CF3SO2)3C] - , [(CF3CF2SO2)3C] - , [(CF3CF2CF2SO2)3C] - , [(CF3CF2CF2CF2SO2)3C] -, [CF3CF2CF2CF2SO3] - , [CF3CF2CF2SO3] - , [(CF3CF2SO2)3C] - , [(SO2CF3)3N] - , [(SO2CF2CF3]2N] - , [((CF3)C6H4)SO3] - , [SO3((CF2CF2CF2CF2)SO3] 2- Examples of anions containing B include [B(C6F5)4] - , [(C6H5)B((CF3)2C6H3)3] - , [(C6H5)B(C6F5)3] - Examples of Ga-containing anions include [((CF3)4Ga)] - , [Ga(C6F5)4] - Examples of anions containing Al include [((CF3)3CO)4Al] - , [((CF3CF2)3CO)4Al] - Examples include:

[0063] When the dental composite resin of the present invention contains a (C) photoacid generator, the content of the (C) photoacid generator is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the total amount of the (A) polymerizable monomers. If the amount of the photoacid generator is less than 0.1 part by mass, the expected polymerization-accelerating ability may not be exhibited, resulting in insufficient curing. If the amount is more than 5 parts by mass, sufficient curing properties may be exhibited, but the ambient light stability may be reduced, shortening the working time, or discoloration may increase, such as the cured product turning brown.

[0064] The photoacid generators that can be used in the dental composite resin of the present invention are not limited to the photoacid generators shown as specific examples, and two or more types can be used in combination.

[0065] The dental composite resin of the present invention may contain, as the photoacid generator (C), only an aryliodonium salt, which is a salt of an aryliodonium cation with an anion having an organic group and one or more atoms of P, B, Al, S, or Ga. The dental composite resin of the present invention may contain, as the photoacid generator (C), only a salt of an aryliodonium cation with an organic group in which at least one H is substituted with F and an anion having one or more atoms of P, B, Al, S, or Ga.

[0066] [(D) Photopolymerization accelerator] The photopolymerization accelerator (D) used in the dental composite resin of the present invention is not particularly limited as long as it has the ability to accelerate polymerization, and known photopolymerization accelerators commonly used in the dental field can be used without any restrictions. Examples of the photopolymerization accelerator (D) that can be used include primary to tertiary amine compounds such as aromatic amine compounds and aliphatic amine compounds, organometallic compounds, and phosphine compounds. Among these, the present invention may contain an aliphatic tertiary amine compound (D1). Furthermore, an organometallic compound may be included because of its good color stability in light.

[0067] Aromatic amine compounds are compounds in which one or more H atoms in ammonia (NH3) are substituted with an aromatic ring. They can be classified as aromatic primary amine compounds when one H atom in NH3 is substituted with an aromatic ring, aromatic secondary amine compounds when one H atom in NH3 is substituted with an aromatic ring and another H atom is substituted with an aromatic ring or an alkyl group, and aromatic tertiary amine compounds when one H atom in NH3 is substituted with an aromatic ring and two other H atoms are substituted with aromatic rings or alkyl groups.

[0068] Specific examples of aromatic primary amine compounds include aniline, etc., specific examples of aromatic secondary amine compounds include N-protected amino acids (esters) such as N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetidine, N-phenylglycine ethyl, and N-phenylglycine, and specific examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, pN,N-dimethyl-toluidine, mN,N-dimethyl-toluidine, pN,N-diethyl-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, and p-dimethylaminobenzoic acid. , p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid 2-butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid amino ester, N,N-dimethylanthranilic acid methyl ester, N,N-dihydroxyethylaniline, N,N-diisopropanolaniline, pN,N-dihydroxyethyl-toluidine, pN,N-dihydroxypropyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-naphthylamine, etc. Among these, p-dimethylaminobenzoic acid ethyl ester is preferred.

[0069] Specific examples of the organometallic compounds include those containing scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), and zirconium (Zr), and preferably those containing tin (Sn), vanadium (V), and copper (Cu). Specific examples of organometallic compounds containing tin (Sn) include dibutyltin diacetate, dibutyltin dimaleate, dioctyltin dimaleate, dioctyltin dilaurate, dibutyltin dilaurate, dioctyltin diversatate, dioctyltin S,S'-bis-isooctylmercaptoacetate, and tetramethyl-1,3-diacetoxydistannoxane. Specific examples of organometallic compounds containing vanadium (V) include acetylacetone. Examples of organic metal compounds containing copper (Cu) include vanadium tetraoxide, vanadium tetroxide, vanadyl acetylacetonate, vanadium oxide stearate, vanadyl oxalate, vanadyl sulfate, oxobis(1-phenyl-1,3-butanedionate)vanadium, bis(maltolate)oxovanadium, vanadium pentoxide, and sodium metavanadate. Specific examples of organometallic compounds containing copper (Cu) include copper acetylacetonate, copper naphthenate, copper octoate, copper stearate, and copper acetate.

[0070] A phosphine compound refers to a compound in which three organic groups are substituted on the P atom, and an aromatic phosphine compound refers to a compound in which a phenyl group, which may have one or more substituents, is substituted on the P atom. Specific examples of the phosphine compound include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri(2-thienyl)phosphine, diphenylpropylphosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, methyldiphenylphosphine, triphenylphosphine, 2-(diphenylphosphino)styrene, 3-(diphenylphosphino)styrene, 4-(diphenylphosphino)styrene, allyldiphenylphosphine, 2-(diphenylphosphino)benzaldehyde, 3-(diphenylphosphino)benzaldehyde, 4-(diphenylphosphino)benzaldehyde, and 2-(phenylphosphino)benzoin. Examples of suitable benzoates include benzoic acid, 3-(phenylphosphino)benzoic acid, 4-(phenylphosphino)benzoic acid, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-(diphenylphosphino)biphenyl, tris(4-fluorophenyl)phosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, 2-(dimethylamino)phenyldiphenylphosphine, 3-(dimethylamino)phenyldiphenylphosphine, 4-(dimethylamino)phenyldiphenylphosphine, 2,2'-bis(diphenylphosphino)biphenyl, and bis[2-(diphenylphosphino)phenyl]ether. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, and tri(p-tolyl)phosphine are preferred.

[0071] Aliphatic amine compounds are compounds in which one or more H groups in ammonia (NH3) are substituted with alkyl groups. The alkyl groups are classified as primary alkyl groups (CH3- or -CH2-), secondary alkyl groups (-CH2- with one H substituted), and tertiary alkyl groups (-CH2- with two H groups substituted). Aliphatic amines are classified as primary amines when one H group in NH3 is substituted with an alkyl group, secondary amines when two H groups in NH3 are substituted with alkyl groups, and tertiary amines when three H groups in NH3 are substituted with alkyl groups.

[0072] Specific examples of aliphatic primary amine compounds include benzhydrylamine, triphenylmethylamine, amino acids such as glycine, or amino acid esters. Specific examples of aliphatic secondary amine compounds include dibenzylamine, N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, N-benzyl-protected amino acids, or N-benzyl-protected amino acid esters. Specific examples of aliphatic tertiary amine compounds include tributylamine, tripropylamine, triethylamine, N,N-Dimethylhexylamine, N,N-Dimethyldodecylamine, N,N-Dimethylstearylamine, N-[3-(dimethylamino)propyl]acrylamide, N,N-Dimethylformamide dimethyl acetal, N,N-Dimethylacetamide dimethyl acetal, N,N-Dimethylformamide diethyl acetal, N,N-Dimethylformamide dipropyl acetal, N,N-Dimethylformamide di-tert-butyl acetal, 1-(2-hydroxyethyl)ethyleneimine, N,N-Dimethylethanolamine, N,N- Dimethylisopropanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N'-(2-hydroxyethyl)-N,N,N'-trimethylethylenediamine, 2-(dimethylamino)-2-methyl-1-propanol, N ,N-Dimethyl-2,3-dihydroxypropylamine, N,N-Diethylethanolamine, 1-Methyl-3-pyrrolidinol, 1-(2-hydroxyethyl)pyrrolidine, 1-Isopropyl-3-pyrrolidinol, 1-Piperidineethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N,N-Dimethylglycine, N,N-Dimethylglycine Methyl, N,N-Diethylglycine Methyl, N,N-Dimethylglycine Ethyl, N,N-Diethylglycine Sodium, 2-(Dimethylamino)ethyl Acetate, N-Methyliminodiacetic Acid, N,Examples include N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, 3-dimethylaminopropionitrile, tris(2-cyanoethyl)amine, N,N-dimethylallylamine, N,N-diethylallylamine, triallylamine, and pentamethylpiperidyl methacrylate.

[0073] The dental composite resin of the present invention may contain (D1) an aliphatic tertiary amine compound as (D) a photopolymerization accelerator. The (D1) aliphatic tertiary amine compound, when combined with (B) a photosensitizer and (C) a photoacid generator, serves as a photopolymerization initiator suitable for dental applications. Examples of the (D1) aliphatic tertiary amine compound include those described above. Preferred examples include N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, pentamethylpiperidyl methacrylate, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, and dibenzylpropanolamine. Among these, pentamethylpiperidyl methacrylate, tribenzylamine, and dibenzylglycine ethyl ester are preferred.

[0074] The dental composite resin of the present invention may contain an aromatic tertiary amine compound as a polymerization accelerator (D). However, if an aromatic tertiary amine compound is contained, the cured dental composite resin may discolor upon exposure to light, resulting in poor color stability. Therefore, when an aromatic tertiary amine compound is contained, it is preferable to contain an ultraviolet absorber. Furthermore, since the dental composite resin of the present invention can exhibit good mechanical properties even without an aromatic tertiary amine compound as a polymerization accelerator (D), it may be possible to eliminate the aromatic tertiary amine compound.

[0075] The type of (D) photopolymerization accelerator can be appropriately selected depending on the types and amounts of other components to be combined. The (D) photopolymerization accelerator can be used alone or in combination of two or more types.

[0076] The amount of (D) photopolymerization accelerator is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total amount of (A) polymerizable monomer contained in the dental composite resin. If the amount of (D) polymerization accelerator is less than 0.2 parts by mass, the polymerization-accelerating ability is poor and curing is likely to be insufficient. If the amount is more than 10 parts by mass, sufficient curing is achieved, but environmental light stability is reduced and discoloration of the cured product may increase.

[0077] The amount of the (D1) aliphatic tertiary amine compound is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of the (A) polymerizable monomer contained in the dental composite resin. If the amount of the (D1) aliphatic tertiary amine compound is less than 0.2 parts by mass, the polymerization-accelerating ability is poor and curing is likely to be insufficient. If the amount is more than 5 parts by mass, sufficient curing is achieved, but environmental light stability is reduced and discoloration of the cured product may increase.

[0078] These polymerization initiators (B) photosensitizer, (C) photoacid generator, and (D) photopolymerization accelerator may be subjected to secondary treatment such as fine pulverization, carrier adsorption, encapsulation in microcapsules, etc. Furthermore, these various types of photopolymerization initiators can be used alone or in combination of two or more types, regardless of the polymerization mode or polymerization method.

[0079] [(E) Filler] The filler (E) used in the present invention can be any known filler that is commonly used, without any restrictions.

[0080] (E) The type of filler is not limited as long as it is a known filler, and a filler suitable for the intended use can be blended, and it is preferable to blend a filler such as an inorganic filler, an organic filler, an organic-inorganic composite filler, or ion-releasing glass. The dental composite resin of the present invention may use the exemplified fillers alone or in combination of two or more types.

[0081] The inorganic filler is not particularly limited in terms of its chemical composition, and specific examples include silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroboroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, fluoroaluminosilicate glass, etc., which are used in dental glass ionomer cements, resin-reinforced glass ionomer cements, resin cements, etc., can also be suitably used. The fluoroaluminosilicate glass referred to here has a basic skeleton of silicon oxide and aluminum oxide, and contains alkali metals for the introduction of non-bridging oxygen. It also contains alkaline earth metals, including strontium, and fluorine as modifying and coordinating ions. Furthermore, it is a composition in which lanthanide series elements are incorporated into the skeleton to impart further radiopacity. Depending on the composition range, these lanthanide series elements are also incorporated into the composition as modifying and coordinating ions.

[0082] Specific examples of organic fillers include polymers such as polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

[0083] Examples of organic-inorganic composite fillers include, but are not limited to, fillers whose surfaces are polymerized and coated with a polymerizable monomer; fillers obtained by mixing and polymerizing a filler and a polymerizable monomer and then pulverizing the mixture to an appropriate particle size; fillers in which a filler is previously dispersed in a polymerizable monomer and then emulsion-polymerized or suspension-polymerized; fillers in which a filler is previously dispersed in a polymerizable monomer and a solvent and then spray-dried and polymerized; and fillers in which a filler is previously dispersed in a solvent and then spray-dried, then impregnated with a polymerizable monomer and then polymerized.

[0084] The ion-releasing glass is characterized by releasing at least one of fluorine ions, strontium ions, borate ions, and aluminum ions, and it is preferable that more than one of these ions be released simultaneously.

[0085] The ion-releasing glass used in the present invention can be any ion-releasing glass without any limitations, as long as it contains one or more glass-skeleton-forming elements that form the glass skeleton and one or more glass-modifying elements that modify the glass skeleton. These ion-releasing glasses can be used alone or in combination. Furthermore, in the present invention, glass amphoteric elements that function as both glass-skeleton-forming elements and glass-modifying elements depending on the glass composition are included in the category of glass-skeleton-forming elements. Specific examples of glass-skeleton-forming elements contained in ion-releasing glasses include silica, aluminum, boron, phosphorus, etc., and these can be used alone or in combination. Specific examples of glass-modifying elements include halogen elements such as fluorine, bromine, and iodine, alkali metal elements such as sodium and lithium, and alkaline earth metal elements such as calcium and strontium, and these can be used alone or in combination. Among these, glass compositions containing silica, aluminum, and boron as glass framework elements and fluorine, sodium, and strontium as glass modifiers are preferred. Specific examples include silica glass, fluoroaluminosilicate glass, fluoroborosilicate glass, and fluoroaluminoborosilicate glass containing strontium and sodium. Furthermore, from the viewpoint of sustained release of fluorine ions, strontium ions, borate ions, and aluminum ions, strontium-containing fluoroaluminoborosilicate glass is more preferred. Specific examples of glass composition ranges include 15-35% by mass of SiO2, 15-30% by mass of Al2O3, 5-20% by mass of BO3, 20-45% by mass of SrO, 5-15% by mass of F, and 0-10% by mass of Na2O. This glass composition can be confirmed using instrumental analysis such as elemental analysis, Raman spectroscopy, and X-ray fluorescence analysis. However, there is no problem with any analytical method as long as the measured values ​​match these composition ranges.

[0086] The manufacturing method of these ion-releasing glasses is not particularly limited, and they can be manufactured by manufacturing methods such as a melting method or a sol-gel method. Among these, a manufacturing method using a melting furnace is preferred from the viewpoint of ease of glass composition design, including raw material selection. The ion-releasing glasses used in the present invention have an amorphous structure, but there is no problem if they contain a partial crystalline structure. Furthermore, there is no problem if they are a mixture of glass having an amorphous structure and glass having a crystalline structure. Whether a glass structure is amorphous or not can be confirmed using analytical equipment such as X-ray diffraction analysis or a transmission electron microscope. Among these, the ion-releasing glasses used in the present invention preferably have an amorphous structure, which is a homogeneous structure, because various ions are gradually released in an equilibrium relationship with the ion concentration in the external environment.

[0087] Furthermore, in order to enhance the ion release from the ion-releasing glass, it is preferable to functionalize the glass surface by surface treatment to improve the ion release. Specific examples of surface treatment materials used for the surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling agents, silane compounds, metal alkoxide compounds, and partial condensates thereof. Among these surface treatment materials, it is preferable to perform a composite surface treatment using an acidic polymer and a silane compound.

[0088] This composite surface treatment is a method in which the surface of ion-releasing glass is coated with a silane compound, and then surface-treated with an acidic polymer, as described in detail below. A silane compound represented by formula (9) is mixed into an aqueous dispersion containing ion-releasing glass that has been finely pulverized to a desired average particle size (D50) by grinding or other methods, and this is hydrolyzed or partially hydrolyzed in the system to form a silanol compound, which is then condensed to form a polysiloxane, which is then coated on the surface of the ion-releasing glass to form polysiloxane-coated ion-releasing glass.

[0089] [Formula (9)] [ka]

[0090] (Wherein, Z is RO - , X is halogen, Y is OH - , R is an organic group having 8 or less carbon atoms, n, m, and L are integers from 0 to 4, and n+m+L=4.

[0091] Specific examples of the silane compound represented by formula (9) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, and silicon hydroxide (silicon oxide hydrate), with tetramethoxysilane and tetraethoxysilane being more preferred.

[0092] A low-condensation silane compound represented by formula (9) is more preferred. For example, a low-condensation silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and tetraethoxysilane is preferred. These compounds can be used alone or in combination. Furthermore, an organosilane compound can also be added as part of the silane compound represented by formula (9) during polysiloxane treatment.

[0093] The most suitable ion-releasing glass can be obtained by subjecting the polysiloxane-coated ion-releasing glass obtained in the previous step to an acidic polymer treatment, in which the glass is reacted with an acidic polymer. The acidic polymer treatment can be carried out using equipment commonly used in the industry, as long as it is a dry-fluidized mixer, such as a Henschel mixer, a super mixer, or a high-speed mixer. The reaction of the acidic polymer with the polysiloxane-coated ion-releasing glass can be carried out by contacting the glass with the acidic polymer solution by impregnation or spraying. For example, the polysiloxane-coated ion-releasing glass can be dry-fluidized, and the acidic polymer solution can be dispersed from above while the glass is still fluidized, followed by thorough stirring. There are no particular restrictions on the method for dispersing the acidic polymer solution, but a drip or spray method is preferred to ensure uniform dispersion. The reaction is preferably carried out near room temperature; as temperatures increase, the reaction between the acid-reactive element and the acidic polymer becomes more rapid, resulting in non-uniform formation of the cement phase.

[0094] It is preferable to remove moisture from the cement reaction phase by heat treatment after the reaction. Residual moisture in the cement reaction phase is detrimental to strength, but the filler of the present invention is reinforced by the covering of a coupling agent condensate film, thereby preventing a decrease in mechanical strength. The heat treatment method after the acidic polymer treatment is not particularly limited and can be performed by a known, general method. Equipment used for the heat treatment is preferably a box-type hot air dryer or a rotary heat treatment device capable of uniform heating. The heat treatment temperature is in the range of room temperature to 200°C, more preferably 40 to 150°C. Temperatures below this range may result in insufficient removal of the aqueous medium, while temperatures above this range may result in decomposition or discoloration of the organic layer of the acidic polymer. The heat treatment time depends on the capacity of the dryer, etc., so there is no problem as long as the time allows sufficient removal of the aqueous medium. After the heat treatment, the heat-treated product can be easily crushed by applying shear or impact force. Crushing can be performed using equipment such as that used for the above reaction.

[0095] The solvent used to prepare the acidic polymer solution used in the reaction can be any solvent that dissolves the acidic polymer, including water, ethanol, and acetone. Among these, water is particularly preferred, as it allows the acidic groups of the acidic polymer to dissociate and react uniformly with the polysiloxane-coated, ion-release glass. The weight-average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2,000 to 50,000, preferably 5,000 to 40,000. Treatment with an acidic polymer having a weight-average molecular weight of less than 2,000 tends to result in an acidic polymer reaction phase not being formed in the polysiloxane-coated, ion-release glass, resulting in reduced ion-release properties. Treatment with an acidic polymer having a weight-average molecular weight greater than 50,000 increases the viscosity of the acidic polymer solution, making it difficult to uniformly treat the polysiloxane-coated, ion-release glass. The acidic polymer concentration in the acidic polymer solution is preferably in the range of 3 to 25% by mass, more preferably 8 to 20% by mass. If the acidic polymer concentration is less than 3% by mass, the acidic polymer reaction phase described above becomes fragile, and the effect of improving ion release cannot be achieved. If the acidic polymer concentration exceeds 25% by mass, it becomes difficult to uniformly diffuse the polysiloxane layer (porous), making it difficult to obtain a homogeneous acidic polymer reaction phase. Furthermore, the reaction occurs immediately upon contact with the polysiloxane-coated ion-releasing glass, resulting in problems such as the formation of strongly reacted aggregates. The amount of acidic polymer solution added to the polysiloxane-coated ion-releasing glass is preferably in the range of 6 to 40% by mass, more preferably 10 to 30% by mass. Based on these addition amounts, the optimal amount of acidic polymer and the optimal amount of water relative to the polysiloxane-coated ion-releasing glass are 1 to 7% by mass and 10 to 25% by mass, respectively.

[0096] The acidic polymer that can be used to form an acidic polymer reaction phase on the surface of the polysiloxane-coated ion-releasing glass by the above method can be any copolymer or homopolymer of a polymerizable monomer having an acidic group such as a phosphate residue, a pyrophosphate residue, a thiophosphate residue, a carboxylic acid residue, or a sulfonic acid group as the acidic group. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, and 11-(meth)acryloyloxydecyl dihydrogen phosphate. Examples of suitable polymers include 2-(meth)acryloyloxyethylphenyl phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethylphenyl phosphonate, di(2-(meth)acryloyloxyethyl)pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogendithiophosphophosphate, and 10-(meth)acryloyloxydecyl dihydrogenthiophosphate. Among the polymers (co)polymerized using these polymerizable monomers, it is preferable to use a homopolymer or copolymer of an α-β unsaturated carboxylic acid, which undergoes a relatively slow acid-base reaction with the acid-reactive element contained in the polysiloxane-coated ion-releasing glass, and specific examples thereof include an acrylic acid polymer, an acrylic acid-maleic acid copolymer, and an acrylic acid-itaconic acid copolymer.

[0097] The above-mentioned (E) filler can be treated with a surface treatment material, typically a silane coupling material, for the purpose of improving its affinity with the polymerizable monomer, its dispersibility in the polymerizable monomer, and the mechanical strength and water resistance of the cured product. The surface treatment material and the surface treatment method are not particularly limited, and known methods can be used without limitation, such as a method of spraying the surface treatment material while stirring the powdered filler, a method of dispersing and mixing the filler and surface treatment material in a solvent, or a method of supplying the silane coupling material in vapor or gas form to the surface of the filler. Preferred silane coupling agents used for surface treatment of fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, and hexamethyldisilazane. In addition to silane coupling agents, surface treatment of fillers can also be performed using titanate-based coupling agents or aluminate-based coupling agents. The amount of surface treatment agent used on the filler is preferably 0.01 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the filler before treatment.

[0098] The shape of the (E) filler is not particularly limited, and fillers of any shape such as spheres, needles, plates, crushed particles, scales, etc. The average particle size of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, and even more preferably 0.1 μm to 10 μm.

[0099] The dental composite resin of the present invention may contain (e) hydrophobic inorganic fine particles as (E) filler. The (e) hydrophobic inorganic fine particles of the present invention preferably have an average primary particle diameter of 1 to 100 nm. The primary particle diameter refers to the diameter of a single particle (primary particle) constituting the powder. Here, the average particle diameter in the present invention can be calculated based on the volume-based particle size distribution measured using, for example, a laser diffraction particle size analyzer, and can be measured using, for example, a laser diffraction particle size analyzer (Microtrac MT3300EXII: manufactured by Nikkiso Co., Ltd.). Alternatively, the primary particle diameter can be measured using dynamic light scattering particle size measurement, or, for particles in which primary particles are strongly aggregated to form secondary particles, using electron micrographs. When particles with a relatively small particle diameter are used, thixotropy can be expected to be exhibited at a small amount due to their large specific surface area. On the other hand, when particles with an average particle diameter of 0.1 to 10 μm are used, a large amount may be required. Methods for hydrophobizing fine particles include surface treatment with modified silicone oil such as dimethylsilicone oil, and / or surface treatment with a silane coupling agent having a trimethylsilyl group, a dimethylsilyl group, a methylsilyl group, or an alkylsilyl group which may have a (meth)acryloyl group having an alkyl chain with 3 to 18 carbon atoms.

[0100] (e) Inorganic particles are preferably used as a carrier for the hydrophobic inorganic fine particles. Examples of such inorganic particles include silica, alumina, zirconia, titanium oxide, ytterbium fluoride, barium sulfate, and composites thereof. It is particularly preferred to use hydrophobic silica fine particles or hydrophobic alumina fine particles having an average primary particle size of 1 to 40 nm.

[0101] Specific examples of hydrophobic silica or alumina fine particles include those manufactured and sold under the trade name Aerosil by Nippon Aerosil Co., Ltd., such as Aerosil R972, Aerosil R974, Aerosil R976, Aerosil R711, Aerosil R7200, Aerosil R976S, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, Aerosil AluC805, Aerosil R8200, Aerosil R104, Aerosil R106, Aerosil RY200, Aerosil RX200, Aerosil RX300, Aerosil RY200S, Aerosil RA200H, and Aerosil RA200HS.

[0102] The amount of (e) hydrophobic inorganic fine particles to be blended is 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of (A) polymerizable monomer. If the amount is less than 0.5 part by mass per 100 parts by mass of (A) polymerizable monomer, the rheological properties of the dental composite resin may not be expected to be exhibited, whereas if the amount exceeds 30 parts by mass, the dental composite resin may become significantly thicker, resulting in a poor feel when used.

[0103] The dental composite resin of the present invention preferably contains a filler (E), and the total amount of the filler (E) and hydrophobic inorganic fine particles (e) is preferably 100 to 400 parts by mass per 100 parts by mass of the polymerizable monomer (A). (E) has a larger average particle diameter than (e). Furthermore, incorporating a large amount of hydrophobic inorganic fine particles (e) can result in increased viscosity of the dental composite resin, which can reduce operability. Therefore, for the purpose of improving the strength of the dental composite resin, inorganic fillers with an average particle diameter of 0.1 to 10 μm are preferably used because they have a low viscosity-increasing effect per blend amount. Furthermore, the filler (E) can be incorporated for purposes other than increasing strength, such as providing radiographic contrast, ion-release properties, color compatibility, color matching, improved adhesion, and improved operability. When the total amount of (E) filler and (e) hydrophobic inorganic fine particles is 100 parts by mass or more per 100 parts by mass of (A) polymerizable monomer, an improvement in the strength of the hardened dental composite resin can be expected.

[0104] The dental composite resin of the present invention may contain a chemical polymerization initiator. Examples of organic peroxides as chemical polymerization initiators include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxydicarbonates, and hydroperoxides. Specific examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Specific examples of peroxyesters include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. Specific examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne. Specific examples of peroxyketals include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-(t-butylperoxy)pallate, and 1,1-di(t-amylperoxy)cyclohexane. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.Specific examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate. Specific examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0105] The dental composite resin of the present invention may use the above-mentioned organic peroxides alone or in combination of two or more. Among these organic peroxides, benzoyl peroxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are preferred from the viewpoint of curing properties.

[0106] From the viewpoint of improving curability, the amount of organic peroxide used as a chemical polymerization initiator is preferably set to 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, per 100 parts by mass of the total amount of polymerizable monomer (A). If the amount of organic peroxide is more than 5 parts by mass, it may be difficult to ensure sufficient operation time, while if the amount of organic peroxide is less than 0.1 part by mass, the mechanical strength may be insufficient.

[0107] The dental composite resin of the present invention may further contain a chemical polymerization accelerator to improve curing properties. Examples of chemical polymerization accelerators include fourth-period transition metal compounds, thiourea derivatives, aliphatic amines, aromatic amines, sulfinic acid and its salts, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, barbituric acid derivatives, triazine compounds, and halogen compounds. The amount of the chemical polymerization accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers.

[0108] The fourth period transition metal compound used as a chemical polymerization accelerator refers to a metal compound from groups 3 to 12 of the fourth period of the periodic table. Specifically, any metal compound of scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), or zinc (Zn) can be used without limitation. Each of the above transition metal elements can have multiple valences, but any valence that allows stable existence can be added to the dental composite resin of the present invention. Examples include Sc (trivalent), Ti (tetravalent), V (tri-, tetra-, or pentavalent), Cr (di-, tri-, or hexavalent), Mn (di- to heptavalent), Fe (di- or trivalent), Co (di- or trivalent), Ni (divalent), Cu (mono- or divalent), and Zn (divalent). Specific examples of transition metal compounds include scandium compounds such as scandium iodide (trivalent), titanium compounds such as titanium chloride (tetravalent) and titanium (tetravalent) tetraisopropoxide, and vanadium compounds such as vanadium acetylacetonate (trivalent), divanadium tetroxide (tetravalent), vanadyl acetylacetonate (tetravalent), vanadium stearate oxide (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis(1-phenyl-1,3-butanedionate)vanadium (tetravalent), and bis(maltolato)oxovanadium (tetravalent). ), vanadium pentoxide (5), sodium metavanadate (5), etc.; manganese compounds include manganese acetate (2), manganese naphthenate (2); iron compounds include iron acetate (2), iron chloride (2), iron acetate (3), iron chloride (3); cobalt compounds include cobalt acetate (2), cobalt naphthenate (2); nickel compounds include nickel chloride (2); copper compounds include copper chloride (1), copper bromide (1), copper chloride (2), copper acetate (2); zinc compounds include zinc chloride (2), zinc acetate (2).

[0109] Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred, with trivalent or tetravalent vanadium compounds being more preferred due to their higher polymerization-promoting ability, and tetravalent vanadium compounds being most preferred. These fourth-period transition metal compounds may be used in combination with one another as needed. The amount of transition metal compound blended is preferably 0.0001 to 1 part by mass per 100 parts by mass of the total amount of (A) polymerizable monomers. Less than 0.0001 part by mass of the transition metal compound may result in insufficient polymerization-promoting effect, while more than 1 part by mass may cause discoloration or gelation of the dental composite resin, resulting in reduced storage stability.

[0110] Any known thiourea derivative can be used as a chemical polymerization accelerator without limitation. Specific examples include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, and dicyclohexylthiourea. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. If necessary, multiple types of these thiourea derivatives may be used in combination. The amount of the thiourea derivative to be blended is preferably 0.1 to 5 parts by mass per 100 parts by mass of the total amount of the polymerizable monomer (A). If the amount is less than 0.1 part by mass, the polymerization-promoting ability may be insufficient, and if the amount is more than 5 parts by mass, the storage stability may decrease.

[0111] Examples of sulfinic acids and their salts 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-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, 2, Examples thereof include sodium 4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, and calcium 2,4,6-triisopropylbenzenesulfinate, with sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate being particularly preferred.

[0112] Specific examples of borate compounds having one aryl group per molecule include trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)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-butylphenyl)boron, Examples of suitable alkyl groups include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like).Specific examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi(3,5-bistrifluoromethyl)phenylboron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, and dialkyldi(p-butyloxyphenyl). )boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.Specific examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri(3,5-bistrifluoromethyl)phenylboron, 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( Examples of suitable alkyl groups include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (wherein the alkyl group is one selected from an n-butyl group, an n-octyl group, an n-dodecyl group, etc.).Specific examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, 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, and tetrakis(m Examples of the methyl quinolinium salt include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of (m-octyloxyphenyl)triphenylboron, (p-octyloxyphenyl)triphenylboron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and (p-octyloxyphenyl)triphenylboron.

[0113] Among these aryl borate compounds, it is more preferable to use a borate compound having three or four aryl groups in one molecule from the viewpoint of storage stability. Furthermore, these aryl borate compounds can be used alone or in combination of two or more.

[0114] Examples of sulfur-containing reducing inorganic compounds include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0115] Examples of the nitrogen-containing reducing inorganic compound include nitrites, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

[0116] Barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric 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, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propyl ... Examples of the salts of barbituric acids include pyrubarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric 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 (preferably salts of alkali metals or alkaline earth metals). Specific examples of the salts of these barbituric acids include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0117] Specific examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

[0118] The dental composite resin of the present invention may be free of a chemical polymerization initiator and a chemical polymerization accelerator. The dental composite resin of the present invention may be free of a polymerization initiator system other than a photopolymerization system.

[0119] <Other ingredients> The dental composite resin of the present invention may also contain components other than the above components (A) to (E), such as fillers typified by fumed silica, benzophenone-based and benzotriazole-based UV absorbers, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and 2,5-ditertiarybutyl-4-methylphenol, chain transfer agents such as α-alkylstyrene compounds, mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene, metal capture agents such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents, discoloration inhibitors, antibacterial agents, color pigments, water and solvents miscible with water in any ratio, and other conventionally known additives.

[0120] The method for preparing the dental composite resin of the present invention is not particularly limited. A common method for producing a dental composite resin is to prepare a matrix by mixing (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and then knead this matrix with (E) a filler and remove air bubbles under vacuum to prepare a uniform paste. The present invention can also be produced using the above-mentioned production method without any problems.

[0121] The dental composite resin of the present invention may contain only (A) the polymerizable monomer, (B) the photosensitizer, (C) the photoacid generator, (D) the photopolymerization accelerator, and (E) the filler, or may contain only one or more of the above components as components other than (A) to (E).

[0122] The dental composite resin kit of the present invention includes at least two of the above-mentioned dental composite resins. In the present invention, when the contrast ratios of the two dental composite resins included in the dental composite resin kit, i.e., the first dental composite resin and the second dental composite resin, are measured at a thickness of 1 mm, the difference in contrast ratio is within 0.3, and each contrast ratio is 0.3 to 0.75.

[0123] The contrast ratio is a measure of transparency and is calculated using the Y value, which is related to brightness among the tristimulus values ​​of the XYZ color system specified in JIS Z8701. Specifically, in the present invention, a 1.0 mm thick sample plate is placed in contact with a black background and a white background, and the Y value of the reflected light when irradiated with standard light C is read. If Y in the case of a black background is Yb and Y in the case of a white background is Yw, the contrast ratio (C) can be calculated from Yb / Yw. The closer the C value is to 1, the more opaque the material is, and the closer it is to 0, the more transparent the material is.

[0124] When the difference in contrast ratio between the first and second dental composite resins is greater than 0.3, laminating the composite resin with the lower contrast ratio on top may achieve aesthetic restoration similar to commercially available kits (e.g., enamel shades, body shades), but when the two composite resins are reversed, the color tone of the composite resin with the higher contrast ratio located on top becomes dominant, making it difficult to reproduce a wide range of colors. After extensive research into these issues, we have found that by keeping the difference in contrast ratio within 0.3, a wide range of colors can be reproduced even when the two composite resins are reversed. In the present invention, the difference in contrast ratio between the first and second dental composite resins is preferably within 0.25, and more preferably within 0.2.

[0125] Furthermore, if the contrast ratio of the first dental composite resin and the second dental composite resin is outside the range of 0.3 to 0.75, it will be impossible to reproduce the translucency to slightly opaque appearance of natural teeth. In the present invention, the contrast ratio of the first dental composite resin and the second dental composite resin is preferably 0.35 to 0.75, and most preferably 0.35 to 0.7.

[0126] In the present invention, the first dental composite resin hardened body L having a thickness of 1 mm is * a * b * The color tone in the space is measured against a white background (L1 * , a1 * , b1 * ) and the L of the hardened body of the second dental composite resin with a thickness of 1 mm * a * b * The color tone in the space is measured against a white background (L2 * , a2 * , b2 * ), the color difference ΔE expressed by the following formula (1) is 2 or more. Equation (1): ΔE = {(L1 * -L2 * ) 2 +(a1 * -a2 * ) 2 +(b1 * -b2 * ) 2} 1 / 2 If ΔE is less than 2, the difference in color tone between a single-layer filling using only one dental composite resin and a multi-layer filling using the first and second dental composite resins is small, making it difficult for the surgeon to recognize the color tone difference and making it impossible to reproduce a wide range of color tones. ΔE must be 2 or more, preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and most preferably 10 or more.

[0127] In the dental composite resin kit of the present invention, the first dental composite resin and the second dental composite resin may satisfy a predetermined relationship between lightness difference and chroma difference in their hardened bodies. Specifically, the first dental composite resin and the second dental composite resin may be a laminate of a 0.3 mm thick hardened body of one dental composite resin and a 0.7 mm thick hardened body of the other dental composite resin, with the 0.3 mm thick hardened body of the dental composite resin facing outwards. * a * b * The color tone in the space is measured against a white background (L S1 * , a S1 * , b S1 * ) and a hardened dental composite resin with a thickness of 0.7 mm was placed on the front side. * a * b * The color tone in the space is measured against a white background (L S2 * , a S2 * , b S2 * ), the brightness difference ΔL expressed by the following formula (2) * 1 and the saturation difference ΔC expressed by the following formula (3) * The dental composite resin kit can be one in which 1 satisfies the relationship of the following formula (4). Formula (2): ΔL * 1=|L S1 * -L S2 * | Equation (3):ΔC * 1=|{(a S1 * ) 2 +(b S1 * ) 2} 1 / 2 -{(a S2 * ) 2 +(b S2 * )2} 1 / 2 | Equation (4): ΔL * 1<ΔC * 1 In general, it is considered most desirable in restorative treatment to match the lightness of the restoration to that of the area to be restored. For this reason, the smaller the change in lightness when swapping the cavity floor and surface sides of the composite resin during layer filling, the easier it is for the surgeon to select the color tone. On the other hand, in order to accommodate the various colors of natural teeth, it is necessary to be able to reproduce a wide range of colors, so a certain degree or more of change in saturation is required when swapping the cavity floor and surface sides of the composite resin during layer filling. Specifically, as shown in equation (4), ΔL * 1<ΔC * 1 and ΔL * 1<ΔC * 1-0.5 is preferred, and ΔL * 1<ΔC * A value of 1-1.0 is most preferable.

[0128] In this case, it is preferable that the first dental composite resin and the second dental composite resin also satisfy the predetermined relationship of lightness difference and chroma difference in the laminate of the 0.3 mm thick hardened body of the other dental composite resin and the 0.7 mm thick hardened body of one dental composite resin. * a * b * The color tone in the space is measured against a white background (L S3 * , a S3 * , b S3 * ) and a hardened dental composite resin with a thickness of 0.7 mm was placed on the front side. * a * b * The color tone in the space is measured against a white background (L S4 * , a S4 * , b S4* ), The brightness difference ΔL is expressed by the following formula (5): * 2 and the saturation difference ΔC expressed by the following formula (6) * 2 preferably satisfies the relationship of the following formula (7). Equation (5): ΔL * 2=|L S3 * -L S4 * | Equation (6):ΔC * 2=|{(a S3 * ) 2 +(b S3 * ) 2} 1 / 2 -{(a S4 * ) 2 +(b S4 * ) 2} 1 / 2 | Equation (7): ΔL * 2<ΔC * 2 In this case, with respect to equation (7), ΔL * 2<ΔC * 2-0.5 is preferable, and ΔL * 2<ΔC * A ratio of 2-1.0 is most preferable.

[0129] In the present invention, it is preferable that at least one of the first dental composite resin and the second dental composite resin has a light diffusion index of 1 mm or more in a cured product. The light diffusion index in the present invention is represented by D, which is calculated by the following formula. D={(I20 / cos20゜)+(I70 / cos70゜)} / (2×I0) (In the formula, I represents the luminous intensity of light transmitted through the sample, and I0, I20, and I70 represent the luminous intensity (light intensity) at angles of 0 degrees, 20 degrees, and 70 degrees, respectively, relative to the direction perpendicular to the sample plate (the direction of incident light).) Since the dental composite resin filled in the restoration area easily blends in with the surrounding color tone, the light diffusion index is preferably 1 or more, more preferably 19 or more, and most preferably 26 or more.

[0130] The dental composite resin kit of the present invention is sufficient as long as it contains at least the above-mentioned first dental composite resin and second dental composite resin, and may also include dental composite resins other than the above-mentioned first dental composite resin and second dental composite resin.

[0131] Furthermore, it is preferable that in the dental composite resin kit of the present invention, all of the composite resins included are in the above-mentioned first dental composite resin and second dental composite resin relationship with any of the other composite resins included.

[0132] Furthermore, when the dental composite resin kit of the present invention contains three or more dental composite resins, it is preferable that any one dental composite resin has the above-mentioned first dental composite resin and second dental composite resin relationship with all other dental composite resins. [Example]

[0133] Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0134] The materials used in the examples and comparative examples and their abbreviations are shown below. [(A) Polymerizable Monomer] BisGMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane in which the average number of moles of ethoxy groups added is 2.6 UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate NPG: Neopentyl glycol dimethacrylate TEGDMA: Triethylene glycol dimethacrylate GDMA: Glycerin dimethacrylate MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[0135] [(B) Photosensitizer] CQ: Camphorquinone MAPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide

[0136] [(C) Photoacid generator] <Salt of an aryliodonium cation and an anion having an organic group in which at least one H is substituted with F and one or more atoms of P, B, Al, S, and Ga> C1: Bis(4-tert-butylphenyl)iodonium nonafluorobutanesulfonate [ka] C2: Bis(4-tert-butylphenyl)iodonium tris(pentafluoropropyl)trifluorophosphate [ka] C3: p-Cumenyl(p-tolyl)iodonium tris(pentafluoroethyl)trifluorophosphate [ka] C4: p-Cumenyl(p-tolyl)iodonium tetrakis(pentafluorophenyl)borate [ka] C5: Bis[4-(tert-butyl)phenyl]iodonium tetra(nonafluoro-tert-butoxy)aluminate [ka] C6: Bis[4-(tert-butyl)phenyl]iodonium tetra(pentafluorophenyl)gallate [ka] <Salt of an anion having an organic group and one or more atoms of P, B, Al, S, or Ga, and an aryl iodonium cation> C11: Bis(4-tert-butylphenyl)iodonium-p-toluenesulfonate [ka] <Photoacid generators that are not salts of an anion having an organic group and one or more atoms of P, B, Al, S, or Ga, and an aryl iodonium cation> C21: Diphenyliodonium hexafluorophosphate [ka] C22: 2,4,6-tris(trichloromethyl)-1,3,5-triazine [ka] C23: Diphenyliodonium-2-carboxylate monohydrate [ka]

[0137] [(D) Polymerization accelerator] <Aliphatic tertiary amine> <<Aliphatic tertiary amine compounds that do not have a primary hydroxyl group>> DMAEMA: N,N-dimethylaminoethyl methacrylate DEAEMA: N,N-diethylaminoethyl methacrylate TBA: Tribenzylamine PMPM: Pentamethylpiperidyl methacrylate DBAP: Dibenzylaminopropanol <<Aliphatic tertiary amine compounds with two or more primary hydroxyl groups>> MDEOA: Methyldiethanolamine TEA: Triethanolamine <Aromatic tertiary amine compounds> DMBE: Ethyl N,N-dimethylaminobenzoate

[0138] [(E) Filler] The manufacturing method of each filler used in preparing the dental composite resin is shown below.

[0139] (Filler E1) To 100.0 g of calcium fluoroaluminosilicate glass (average particle size 1.1 μm), 50.0 g of water, 35.0 g of ethanol, and 3.0 g of 3-methacryloyloxypropyltrimethoxysilane (a silane coupling agent) were stirred at room temperature for 2 hours, and the resulting silane coupling treatment solution was added and stirred for 30 minutes. The mixture was then heat-treated at 100°C for 15 hours to obtain filler E1.

[0140] (Filler E2) To 100.0 g of zirconium silicate filler (average particle size 0.8 μm: zirconia 85 wt%, silica 15 wt%), 50.0 g of water, 35.0 g of ethanol, and 5.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the resulting silane coupling treatment liquid was added and stirred for 30 minutes. Then, the mixture was heat-treated at 100 ° C for 15 hours to obtain filler E2.

[0141] (Filler E3) The raw materials silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate were mixed and then melted at 1400°C to obtain Glass A (glass composition: SiO2: 22.5% by mass, Al2O3: 20.0% by mass, BO3: 12.3% by mass, SrO: 35.7% by mass, Na2O: 2.5% by mass, F: 7.0% by mass). The resulting Glass A was then pulverized using a vibration mill for 100 hours and then further pulverized using a wet bead mill for 3 hours. To 100 g of the resulting pulverized material, 4.5 g of a low-condensation silane compound "MKC Silicate MS56S" (SiO2 content 56.0% by mass, degree of polymerization 2-100, manufactured by Mitsubishi Chemical Corporation) was added and stirred for approximately 90 minutes. After mixing for the specified time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held there for 6 hours, and then cooled to obtain a heat-treated product. The resulting heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. After crushing, a polysiloxane-treated product with good fluidity was obtained. (acid polymer treatment) 100 g of the polysiloxane-treated product was placed in a Henschel mixer, and while stirring, 16.0 g of an aqueous polyacrylic acid solution (polymer concentration 13% by mass, weight-average molecular weight 20,000: manufactured by Nakarai, Inc.) was sprayed from above. After spraying, the powder was removed from the mixer and heated at 100°C for 3 hours in a hot air dryer to obtain a polysiloxane-polyacrylic acid-treated product. (Silane treatment) To 100g of the polysiloxane-polyacrylic acid treated product, 100.0g of water, 80.0g of ethanol, 0.003g of phosphoric acid, and 12.0g of 8-methacryloyloxypropyltrimethoxysilane (silane coupling agent) were stirred at room temperature for 2 hours, and the resulting silane coupling treatment solution was added and stirred for 30 minutes. After that, the mixture was heat-treated at 100°C for 15 hours to obtain filler E3 (average particle size 1.0μm).

[0142] (Filler E4) Filler E4 (average particle size 0.4 μm) was obtained by extending the wet bead milling time for Filler E3 and following the same procedures as above.

[0143] (Filler E5) After mixing various raw materials, including silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate, the mixture was melted at 1400°C to obtain glass (glass composition: 22.5% by mass of SiO, 20.0% by mass of AlO, 12.3% by mass of BO, 35.7% by mass of SrO, 2.5% by mass of NaO, 7.0% by mass of F). The obtained glass was then pulverized for 100 hours using a vibration mill, and then further pulverized for 3 hours using a wet bead mill. (Polysiloxane treatment) To 100 g of the resulting pulverized material, 4.5 g of a low-condensation silane compound "MKC Silicate MS56S" (SiO2 content 56.0 mass%, degree of polymerization 2-100, manufactured by Mitsubishi Chemical Corporation) was added, and the mixture was stirred and mixed for approximately 90 minutes. After mixing for the specified time, the resulting treated slurry was aged at 50°C for 40 hours in a hot air dryer, then heated to 150°C and held for 6 hours, and then cooled to obtain a heat-treated product. The resulting heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. After crushing, a polysiloxane-treated product with good fluidity and a surface coated with polysiloxane was obtained. (Silane treatment) To 100 g of the polysiloxane treatment product, 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 3-methacryloyloxypropyltrimethoxysilane (a silane coupling agent) were stirred at room temperature for 2 hours, and the resulting silane coupling treatment solution was added and stirred for 30 minutes. The mixture was then heat-treated at 90°C for 15 hours to obtain filler E5 (average primary particle size: 1.0 μm).

[0144] (Filler E6) Filler E6 (average particle size 0.4 μm) was obtained by extending the wet bead milling time for Filler E3 and following the same procedures as in the other steps.

[0145] (Filler E7) Filler E7 (average particle size 3.0 μm) was obtained by shortening the wet bead milling time for Filler E3 and following the same procedures as above.

[0146] (Filler E8) Filler E8 (average particle size 10 μm) was obtained by shortening the wet bead milling time for Filler E7 and following the same procedures as above.

[0147] <(e) Hydrophobic inorganic fine particles> Filler e1: Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) Filler e2: Aerosil R8200 (manufactured by Nippon Aerosil Co., Ltd.) Filler e3: Aerosil R711 (manufactured by Nippon Aerosil Co., Ltd.) Filler e4: Aerosil AluC805 (manufactured by Nippon Aerosil Co., Ltd.) Filler e5: Aerosil R805 (manufactured by Nippon Aerosil Co., Ltd.)

[0148] [UV absorber] BT: 2-(2-hydroxy-5-methylphenyl)benzotriazole [Polymerization inhibitor] MeHQ: p-Methoxyphenol [Fluorescent agent] FA: Diethyl 2,5-dihydroxyterephthalate

[0149] The test methods employed in the examples and comparative examples are as follows.

[0150] (1) Color measurement of dental composite resin Dental composite resin was filled into a stainless steel mold (15φ x 1mm: disc-shaped), and a cover glass was placed on top and pressed against a glass plate. The resin was cured by irradiating it with light using a photopolymerization irradiator (Grip Light II, manufactured by Matsufuku) for 1 minute. The cured product was then removed from the mold, the cover glass removed, and the color of the specimen was measured. The specimen was placed against a standard white background (D65 / 10°, X = 81.07, Y = 86.15, Z = 93.38) and measured using a spectrophotometer (manufactured by BYK) under specified, consistent conditions (light source: C, viewing angle: 2°, measurement area: 11 mm). The color difference between the dental composite resins included in the kit is the L of the first dental composite resin 1mm thick hardened body. * a * b * The color tone in the space is measured against a white background (L1 * , a1 * , b1 * ) and the L of the hardened body of the second dental composite resin with a thickness of 1 mm * a * b * The color tone in the space is measured against a white background (L2 * , a2 * , b2 * ) and expressed as ΔE calculated by the following formula (1). Equation (1): ΔE = {(L1 * -L2 * ) 2 +(a1 * -a2 * ) 2 +(b1 * -b2 * ) 2} 1 / 2 Here, if ΔE is low, there is little difference in color tone between single-layer filling and stacked filling of multiple colors, so ΔE must be 2 or more, preferably 3 or more, more preferably 4 or more, and most preferably 5 or more.

[0151] (2) Color measurement assuming layered filling After filling a stainless steel mold (15φ x 0.3mm, disc-shaped) with dental composite resin, excess dental composite resin was removed by scraping until the composite was the same thickness as the mold. With the top open, the resin was cured by irradiating it with light using a light-curing irradiator (Grip Light II, manufactured by Matsufu) for 1 minute. The cured product was then removed from the mold and fitted into a stainless steel mold (15φ x 1mm, disc-shaped). Another dental composite resin was poured over the fitted cured product, and a cover glass was placed on top and pressed against the mold using a glass plate. The cover glass was then irradiated with light using a light-curing irradiator (Grip Light II, manufactured by Matsufu) for 1 minute until the cured product was removed from the mold. The color of the specimen was measured. The color measurement was performed by placing the test specimen on a background of a standard white board (D65 / 10°X=81.07, Y=86.15, Z=93.38) and using a spectrophotometer (manufactured by BYK-Chemie) under predetermined conditions (light source: C, viewing angle: 2°, measurement area: 11 mm). The laminated cured product was measured twice, once with the front and back facing the spectrophotometer side and the back facing the standard white plate, and the difference in lightness ΔL* and the difference in saturation ΔC* were calculated using the following formula. Formula (2): ΔL * 1=|L S1 * -L S2 * | Equation (3):ΔC * 1=|{(a S1 * ) 2 +(b S1 * ) 2} 1 / 2 -{(a S2 * ) 2 +(bS2 * ) 2} 1 / 2 | In addition, saturation C * is C * ={(a * ) 2 +(b * ) 2} 1 / 2 It is calculated as follows.

[0152] Here, of the surfaces facing each other in the lamination direction, the surface that was filled first when preparing the cured product is referred to as the reference surface, and the surface that was filled later is referred to as the lamination surface. When the reference surface is the front, the color measurement result (L S1 * , a S1 * , b S1 * On the other hand, when the reference surface is the back, the color measurement result is (L S2 * , a S2 * , b S2 * ) In general, it is considered most desirable in restorative treatment to match the brightness of the restoration to that of the area to be restored. For this reason, the smaller the change in brightness when swapping the cavity floor and surface sides of the composite resin during layer filling, the easier it is for the surgeon to select the color tone. On the other hand, in order to accommodate natural teeth with various colors, it is necessary to be able to reproduce a wide range of colors, so a certain degree or more of change in saturation is required when swapping the cavity floor and surface sides of the composite resin during layer filling. Specifically, Equation (4): ΔL * 1<ΔC * 1 and ΔL * 1<ΔC * 1-0.5 is preferred, and ΔL * 1<ΔC * 1-0.6 is more preferable, and ΔL * 1<ΔC * 1-0.7 is more preferable, and ΔL *1<ΔC * A value of 1-1.0 is most preferable.

[0153] (3) Contrast ratio measurement The prepared dental composite resin was filled into a stainless steel mold (15mm diameter x 1mm, disc-shaped), and then a cover glass was placed on top and pressed against a glass plate. The resin was cured by irradiating the cover glass with light using a photopolymerization irradiator (Grip Light II, manufactured by Matsufuku) for 1 minute. The cured product was then removed from the mold, the cover glass removed, and the color of the specimen was measured. The specimen was placed against a standard white background (D65 / 10°, X = 81.07, Y = 86.15, Z = 93.38) and measured using a spectrophotometer (manufactured by BYK) under the specified conditions (light source: C, viewing angle: 2°, measurement area: 11 mm). The Y value was designated as Yw (white background). The test specimen was placed on a standard black background (D65 / 10°X=0.0, Y=0.0, Z=0.0) and measured using a spectrophotometer (BYK) under specified conditions (light source: C, viewing angle: 2°, measurement area: 11 mm), and the Y value was taken as Yb (black background). The contrast ratio was expressed as C / N, calculated using the following formula: C / N=Yb(black background) / Yw(white background) Here, the C / N ratio must be translucent to slightly opaque, similar to natural teeth, and should be 0.3–0.75, preferably 0.35–0.75, and most preferably 0.35–0.7. Furthermore, if the contrast ratio difference between composite resins used in layered filling exceeds 0.3, layering the composite resin with a lower contrast ratio on top can achieve aesthetic restorations similar to commercially available kits (e.g., enamel shades, body shades), but if the composite resins are reversed during layered filling, the color of the composite resin with a higher contrast ratio will dominate, making it difficult to reproduce a wide range of colors. A contrast ratio difference of 0.3 or less allows for a wide range of color reproduction, even when the composite resins are reversed during layered filling. For this reason, the contrast ratio difference should be within 0.3, preferably within 0.25, and most preferably within 0.2.

[0154] (4) Transmitted light spectrometry The prepared dental composition was filled into a stainless steel mold (15φ x 1mm: disc-shaped), cover glasses were placed on both sides, and the mold was pressed against a glass mixing plate. The paste was then cured by irradiating five locations per sample with spot light for 30 seconds using a photopolymerization irradiator (Grip Light II, manufactured by Shofu Co., Ltd.). After curing, the cured product was removed from the mold and attached to a measuring jig on a three-dimensional goniophotometer (GP-200, manufactured by Murakami Color Research Laboratory Co., Ltd.) to measure the distribution of transmitted light intensity from +90° to -90° around the incident direction. The light diffusion coefficient (D) was calculated using the following formula: D={(I20 / cos20゜)+(I70 / cos70゜)} / (2×I0) (In the formula, I represents the luminous intensity of light transmitted through the sample, and I0, I20, and I70 represent the luminous intensity (light intensity) at angles of 0 degrees, 20 degrees, and 70 degrees, respectively, relative to the direction perpendicular to the sample plate (the direction of incident light).) Here, the optical diffusion index is preferably 1 or more, more preferably 19 or more, and most preferably 26 or more, so that the dental composite resin filled in the restoration area blends easily with the surrounding color tone.

[0155] <Manufacturing method for dental composite resin> All ingredients except for (E) filler shown in Table 1 were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mix rotor to obtain a matrix. The matrix, (E) filler, and any trace colorant were then placed in a kneader, mixed uniformly, and degassed under vacuum to obtain a dental composite resin paste. In Table 1, the abbreviation for each component is followed by the mass part of each component in parentheses.

[0156] [Table 1]

[0157] <Measurement of contrast ratio, color tone, and light diffusion> For each dental composite resin produced, the contrast ratio, color tone, and light diffusion index of the cured product were measured according to the methods described above. The measurement results are shown in Table 2. Note that for Composition 13, the contrast ratio was 1.00 (opaque), so the diffused light was not measured. [Table 2]

[0158] <Evaluation of color compatibility in single-layer filling> The color match of each dental composite resin was evaluated when filled in a single layer. A Class 1 cavity (3 mm diameter, 2 mm depth) was formed in the center of the occlusal surface of artificial teeth (first molars: Verasia SA, manufactured by Shofu Co., Ltd.) of five shades (A1, A2, A3, A3.5, and A4), and the cavity was then bonded with Cera Resin Bond, manufactured by Shofu Co., Ltd. After bonding, the composite resin was filled into the cavity and the paste was cured using a light-curing irradiator. After hardening, the tooth was polished, and five evaluators visually confirmed the color match and rated it on a 5-point scale. The evaluation criteria are as follows. In Table 3, the average scores of the five evaluators are rounded up or down and the results are shown in the "Evaluation" column. 5: The boundary between the artificial tooth and the filled composite resin is not clearly visible, and the colors blend in very well. 4: Although the boundary between the artificial tooth and the filled composite resin is visible, the color tone is consistent. 3: The boundary between the artificial tooth and the filled composite resin is easily visible, but there is an acceptable color match. 2: The boundary between the artificial tooth and the filled composite resin is easily visible, and the color tone is slightly different. 1: The color of the artificial tooth and the filled composite resin are clearly different. If the color of the hardened dental composite resin is close to that of the restored tooth, for example, if the evaluation result is 3 to 5, it can be used in a single-layer filling, and it is also expected that it will be used in a single-layer filling at the discretion of the surgeon.

[0159] [Table 3]

[0160] Table 3 shows the relationship between each dental composite resin, artificial teeth of five shades (A1, A2, A3, A3.5, and A4), and the evaluation results. Compositions 1 to 11 and 14, which have contrast ratios in the range of 0.3 to 0.75, were found to have good color matching with any of the artificial teeth. In particular, compositions 2 to 11 and 14, which were filled with dental composite resins with light diffusing properties, were found to have even better color matching.

[0161] On the other hand, compositions 12 and 13, which are dental composite resins with a contrast ratio outside the range of 0.3 to 0.75, do not have a contrast ratio that is similar to the translucent to slightly opaque value of natural teeth, and therefore have low color compatibility with all artificial teeth A1 to A4 in single-layer fillings. For this reason, even if dental composite resins with such compositions are included in a dental composite resin kit, it will not be possible to create a dental composite resin kit that can reproduce a wide range of colors and perform aesthetic filling restorations, even if the number of dental composite resins is reduced.

[0162] <Color measurement results assuming layered filling> According to the method described in the above "Color Measurement for Layered Filling," two types of dental composite resins were laminated together to produce a cured product for the combinations of dental composite resins shown in the Examples and Comparative Examples in Tables 4 and 5, and the color of the cured product was measured. Furthermore, |ΔL*| and |ΔC*| were calculated based on the measured color. Tables 4-6 show the measurement and calculation results. Note that the calculation results shown in Tables 4-6 may not completely match the measurement results due to significant digits.

[0163] [Table 4]

[0164] [Table 5]

[0165] [Table 6]

[0166] <Evaluation of color compatibility in layered filling> Class 1 cavities (3 mm diameter, 2 mm depth) were created in the center of the occlusal surface of artificial teeth (first molars: Verasia SA manufactured by Shofu Co., Ltd.) in five shades (A1, A2, A3, A4.5, and A4), and adhesive treatment (Cera Resin Bond manufactured by Shofu Co., Ltd.) was performed on the cavities. After adhesive treatment, two composite resins were layered and filled into each cavity, and the paste was hardened using a light-curing irradiator. After hardening, the teeth were polished, and color compatibility was confirmed visually and rated on a 5-point scale. In principle, a light-colored composite resin is used on the surface of a light-colored artificial tooth, and a dark-colored composite resin is used on the surface of a dark-colored artificial tooth. However, in this evaluation, the thicknesses of the two (first and second) composite resins were reversed at 3:7 (0.6 mm:1.4 mm) and 7:3 (1.4 mm:0.6 mm), and the surface / bottom layer was alternated for a total of four fillings. The evaluation of the best color match was adopted. The evaluation value for each example was recorded as the lowest evaluation value among the five filled artificial teeth (A1, A2, A3, A4.5, and A4) as described above. The evaluation criteria were as follows: 5: The boundary between the artificial tooth and the filled composite resin is not clearly visible, and the colors blend in very well. 4: Although the boundary between the artificial tooth and the filled composite resin is visible, the color tone is consistent. 3: The boundary between the artificial tooth and the filled composite resin is easily visible, but there is an acceptable color match. 2: The boundary between the artificial tooth and the filled composite resin is easily visible, and the color tone is slightly different. 1: The color of the artificial tooth and the filled composite resin are clearly different. For multiple restored teeth with different shades, it is expected that the shades can be adjusted by layering and filling multiple dental composite resins.

[0167] [Table 7]

[0168] Table 5 shows the results of the evaluation of color matching in layered filling. All of Examples 1 to 23 were found to have good color matching. Among them, Examples 4 to 22, which were filled with only a dental composite resin having light diffusibility, were found to have better color matching than Examples 1 to 3 and 23, in which at least one dental composite resin was a dental composite resin without light diffusibility.

[0169] On the other hand, the color compatibility of Comparative Examples 1 and 2, in which the ΔE for the two dental composite resins was less than 2, showed little change in color between single-layer filling and multi-layer filling because the color tones of the composite resins were similar, and it was found that the color compatibility for all five types of artificial teeth could not be said to be good.

[0170] In comparison example 3, in which the difference in C / N between the two dental composite resins exceeded 0.3, when composition 9, which has a higher contrast ratio, was layered and filled on top, the color tone of composition 1, which has a lower contrast ratio of more than 0.3, was difficult to reflect, and the color tone of composition 9 became dominant, making it impossible to reproduce a wide range of colors.It was therefore recognized that the color tone compatibility with all five types of artificial teeth was not good.

[0171] In Comparative Examples 4 and 5, which were filled with dental composite resins with a C / N ratio outside the range of 0.3 to 0.75, the C / N was not a translucent to slightly opaque value similar to that of natural teeth, and therefore the color match was poor when filled, and the color appeared to float and not blend in.

[0172] Furthermore, in Examples 1, 3 to 23, where ΔC* is greater than ΔL*, when the composite resin to be filled is switched upside down, the saturation changes but the change in lightness is suppressed, making it easier for the surgeon to estimate the lightness and therefore facilitating the reproduction of tooth color.

[0173] The dental composite resin of the present invention evaluated in the examples can be used without any problems with various known dental materials, such as dental adhesives, dental core construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicures, dental adhesives for fixing loose teeth, dental hard resins, dental cutting materials, and dental 3D printer materials. [Industrial Applicability]

[0174] According to the present invention, a dental composite resin kit can be provided that can reproduce a wide range of colors by using a relatively small number of dental composite resins in combination when performing aesthetic filling and restoration on teeth of various colors.

Claims

1. A kit including at least a first dental composite resin and a second dental composite resin, When the contrast ratios of the first dental composite resin and the second dental composite resin are measured at a thickness of 1 mm, the difference in contrast ratio is within 0.3, and each contrast ratio is 0.3 to 0.75; L of the first dental composite resin hardened body having a thickness of 1 mm * a * b * The color tone in the space is measured against a white background (L １ * , a １ * , b １ * )year, L of the second dental composite resin hardened body having a thickness of 1 mm * a * b * The color tone in the space is measured against a white background (L ２ * , a ２ * , b ２ * ) and A dental composite resin kit having a color difference ΔE represented by the following formula (1) of 2 or more. Equation (1): ΔE = { (L １ * - L ２ * ) ２ + (a １ * - a ２ * ) ２ + (b １ * - b ２ * ) ２} １／２

2. The first dental composite resin and the second dental composite resin are For a laminate of one dental composite resin hardened body having a thickness of 0.3 mm and another dental composite resin hardened body having a thickness of 0.7 mm, The hardened dental composite resin with a thickness of 0.3 mm is placed on the front side. * a * b * The color tone in the space is measured against a white background (L Ｓ１ * , a Ｓ１ * , b Ｓ１ * )year, The hardened dental composite resin with a thickness of 0.7 mm is placed on the front side. * a * b * The color tone in the space is measured against a white background (L Ｓ２ * , a Ｓ２ * , b Ｓ２ * ) and The brightness difference ΔL is expressed by the following formula (2): * 1 and the saturation difference ΔC expressed by the following formula (3) * 2. The dental composite resin kit of claim 1, wherein 1 satisfies the relationship of the following formula (4): Equation (2): ΔL * 1 = |L Ｓ１ * - L Ｓ２ * | Equation (3): ΔC * 1 = |{(a Ｓ１ * ) ２ + (b Ｓ１ * ) ２} １／２ - {(a Ｓ２ * ) ２ + (b Ｓ２ * ) ２} １／２ | Equation (4): ΔL * 1 < ΔC * 1

3. 2. The dental composite resin kit of claim 1, wherein at least one of the first dental composite resin and the second dental composite resin has a light diffusion index of 1 or more when cured at a thickness of 1 mm.

4. The first dental composite resin and the second dental composite resin are Regarding a laminate of the other dental composite resin hardened body having a thickness of 0.3 mm and one dental composite resin hardened body having a thickness of 0.7 mm, The hardened dental composite resin with a thickness of 0.3 mm is placed on the front side. * a * b * The color tone in the space is measured against a white background (L Ｓ３ * , a Ｓ３ * , b Ｓ３ * )year, The hardened dental composite resin with a thickness of 0.7 mm is placed on the front side. * a * b * The color tone in the space is measured against a white background (L Ｓ４ * , a Ｓ４ * , b Ｓ４ * ) and The brightness difference ΔL is expressed by the following formula (5): * 2 and the saturation difference ΔC expressed by the following formula (6) * 2. The dental composite resin kit of claim 2, wherein 2 satisfies the relationship of the following formula (7): Equation (5): ΔL * 2 = |L Ｓ３ * - L Ｓ４ * | Equation (6): ΔC * 2 = |{(a Ｓ３ * )+(b ２ +(b Ｓ３ * )) ２}-{(a １／２ -{(a Ｓ４ * )+(b ２ +(b Ｓ４ * )) ２} １／２ | Equation (7): ΔL * 2 < ΔC * 2

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