Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/15—Compositions characterised by their physical properties
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/15—Compositions characterised by their physical properties
  • A61K6/17—Particle size
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/70—Preparations for dentistry comprising inorganic additives
  • A61K6/71—Fillers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/70—Preparations for dentistry comprising inorganic additives
  • A61K6/71—Fillers
  • A61K6/76—Fillers comprising silicon-containing compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a dental composition. More specifically, the present invention relates to a dental composition that has high mechanical strength, excellent polishability, good paste properties, as well as high adhesive strength to tooth structure.
• filling and restorative materials such as filling composite resins and filling compomers, and crown restorative materials such as metal alloys, porcelain, and resin materials are usually used.
• crown restorative materials both of which may be collectively referred to as "dental restorative materials" in this specification
• various adhesive systems using adhesives have been used to bond tooth tissue and dental restorative materials.
• One of the commonly used adhesive systems is the so-called acid etching type (total etching type) adhesive system, in which the surface of the tooth tissue is etched using an acid etching agent such as an aqueous phosphoric acid solution, and then a bonding agent is applied to bond the tooth tissue and dental restorative material.
• an acid etching agent such as an aqueous phosphoric acid solution
• this type of adhesive system was mainly a two-step adhesive system in which a self-etching primer containing an acidic monomer, a hydrophilic monomer, and water was applied to the surface of the tooth, and then a bonding material containing a cross-linking monomer and a polymerization initiator was applied without rinsing with water.
• a one-step adhesive system using a one-component dental adhesive (one-component bonding material) that combines the functions of a self-etching primer and a bonding material has become widely used.
• One-component bonding materials generally contain acidic monomers, hydrophilic monomers, cross-linking monomers, etc. as monomer components, and water or a hydrophilic volatile organic solvent is generally used.
• bonding materials differ from dental composite resins (self-adhesive dental composite resins, etc.) in that they contain a solvent (water, organic solvent, etc.) and in the amount of filler they contain.
• Self-adhesive dental composite resins generally have issues with their adhesive strength to tooth structure compared to bonding materials.
• a self-adhesive dental composite resin that contains a water-soluble photopolymerization initiator or an asymmetric acrylamide methacrylate compound with a solubility in water of 10 g/L or more at 25°C has been disclosed in order to improve the adhesive strength, which is a characteristic of bonding materials (Patent Documents 4 and 5).
• Patent Documents 1 to 5 contain inventions relating to the adhesive strength of self-adhesive dental composite resins to tooth structure, there is no disclosure of an important characteristic of dental composite resins, that is, the ability to easily obtain a desired smoothness with short polishing times (hereinafter sometimes simply referred to as "ease of polishing").
• the polishability and durability of the lubricity of the cured product tend to improve.
• the viscosity of the paste increases significantly, making it difficult to increase the filler content, resulting in problems such as a decrease in the mechanical strength of the cured product, or a decrease in operability such as the paste being sticky before polymerization.
• the present invention aims to provide a dental composition that has not only high mechanical strength, excellent polishability, and good paste properties after curing, but also excellent adhesion to tooth structure.
• the present invention includes the following inventions.
• the filler (d) includes an aggregated filler (d-1) in which primary particles are aggregated, the primary particles are metal oxides,
• the specific surface area of the aggregated filler (d-1) measured by the BET method is 5 m 2 /g or more and 60 m 2 /g or less.
• the dental composition according to [1], wherein the average particle size of the primary particles of the aggregated filler (d-1) is 30 to 500 nm.
• the filler (d) further comprises a filler (d-2) other than the aggregated filler (d-1).
• the metal oxide of the primary particles of the aggregate filler (d-1) contains Si and Zr elements.
• the content of the aggregate filler (d-1) is 20 to 85 mass% in 100 mass% of the total amount of the dental composition.
• the content of the monomer (a) having an acidic group is 0.1 to 25 mass% in 100 mass% of the total amount of the dental composition.
• the dental composition according to any one of [1] to [10], wherein the aggregate filler (d-1) has a specific surface area measured by a BET method of 5 m 2 /g or more and less than 50 m 2 /g.
• a self-adhesive dental composite resin comprising the dental composition according to any one of [1] to [11].
• a dental cement comprising the dental composition according to any one of [1] to [11].
• a dental composition can be provided which not only exhibits high mechanical strength in the cured product, excellent polishability, and good paste properties, but also has excellent adhesion to tooth structure.
• the present invention can provide a dental composition that is easy to polish and therefore can easily provide a desired smoothness by polishing for less than 20 seconds.
• even when the filler content is high it is possible to achieve both high mechanical strength and excellent ease of polishing of the cured product, and it is also possible to achieve good paste properties and excellent adhesion to tooth structure.
• the dental composition of the present invention contains a monomer (a) having an acidic group, a monomer (b) having no acidic group, a polymerization initiator (c), and a filler (d).
• the filler (d) includes an aggregated filler (d-1) in which primary particles of a metal oxide are aggregated.
• the specific surface area of the agglomerated filler (d-1) measured by the BET method is 5 m 2 /g or more and 60 m 2 /g or less.
• the average particle size of the secondary particles measured by laser diffraction is preferably 1 to 20 ⁇ m.
• (meth)acrylic is a general term for methacrylic and acrylic, and the same applies to similar expressions (such as “(meth)acrylic acid” and “(meth)acrylonitrile”).
• the upper and lower limits of numerical ranges can be appropriately combined.
• the embodiments can be modified by combining some or all of them as appropriate, except in cases where they are particularly inapplicable.
• an aggregated filler with a specific specific surface area which is formed by agglomerating primary particles of metal oxide, it is possible to achieve both excellent ease of polishing (usually smaller particle diameters tend to be more effective) and mechanical strength (usually larger particle diameters tend to be more effective), and furthermore, not only does it have good paste properties, but it also surprisingly has excellent adhesion to tooth structure.
• the dental composition of the present invention provides properties such as ease of polishing and excellent adhesion to tooth structure.
• the monomer component In order for a dental material to have adhesion to tooth structure, the monomer component must come into contact with the tooth structure.
• the monomer components are less likely to come into contact with the tooth structure compared to dental adhesives that contain almost no filler and have a low viscosity, making it difficult to obtain sufficient adhesion to the tooth structure.
• the dental composition of the present invention contains an aggregated filler having a specific BET specific surface area, which is formed by agglomeration of primary particles that are metal oxides.
• the presence of monomer components contained in the gaps between the primary particles can be ignored, and the fluidity of the monomer that exerts adhesion to tooth structure is affected by the BET specific surface area of the agglomerated filler formed by agglomeration of the primary particles.
• the dental composition contains a monomer (a) having an acidic group in order to impart excellent adhesion to tooth structure. By blending the monomer (a) having an acidic group, it becomes possible to provide high adhesive strength to tooth structure.
• a radically polymerizable monomer is preferably used in the dental composition.
• radical polymerizable monomer in the monomer (a) having an acidic group examples include (meth)acrylate monomers, (meth)acrylamide monomers, esters such as ⁇ -cyanoacrylic acid, (meth)acrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, and styrene derivatives.
• (meth)acrylate monomers and (meth)acrylamide monomers are preferred from the viewpoint of curability.
• Examples of the monomer (a) having an acidic group used in the present invention include monomers having at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, or a sulfonic acid group.
• the monomer (a) having an acidic group may be used alone or in appropriate combination of two or more. Specific examples of the monomer (a) having an acidic group are shown below.
• Examples of monomers 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)acryloyloxyoctyl dihydrogen phosphate, and the like.
• Hydrogen 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, bis[2-(meth)acryloyloxy] acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyl
• 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, and their acid chlorides, alkali metal salts, and amine salts.
• 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, thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(
• Monomers having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenyl phosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate, and acid chlorides, alkali metal salts, and ammonium salts thereof.
• Examples of monomers having a carboxylic acid group include (meth)acrylic acid esters having one carboxyl group or its acid anhydride group in one molecule, and (meth)acrylic acid esters having multiple carboxyl groups or their acid anhydride groups in one molecule.
• Examples of monomers having one carboxyl group or its acid anhydride group in one molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate, O-(meth)acryloyltyrosine, and N-(meth)acryloyltyrosine.
• N-(meth)acryloylphenylalanine N-(meth)acryloyl-p-aminobenzoic acid
• N-(meth)acryloyl-o-aminobenzoic acid 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid
• 4-(meth)acryloyloxybenzoic acid N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, and compounds in which the carboxyl group of these compounds has been converted to an acid anhydride group.
• Examples of monomers having multiple carboxyl groups or their acid anhydride groups in one molecule include, for example, 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-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxyethyl trimellitate anhydride ...
• Examples of such compounds include dibutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate, 6-(meth)acryloyloxyethyl naphthalene-1,2,6-tricarboxylic anhydride, 6-(meth)acryloyloxyethyl naphthalene-2,3,6-tricarboxylic anhydride, 4-(meth)acryloyloxyethyl carbonylpropionoyl-1,8-naphthalic anhydride, and 4-(meth)acryloyloxyethyl naphthalene-1,8-tricarboxylic anhydride.
• Examples of monomers having a sulfonic acid group include 2-sulfoethyl (meth)acrylate.
• monomers (a) having an acidic group from the viewpoint of good adhesive strength when used as a self-adhesive dental composite resin, it is preferable to include a monomer having a phosphoric acid group or a monomer having a carboxylic acid group, and examples of such monomers include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl Dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(
• the content of the monomer (a) having an acidic group in the dental composition is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, even more preferably 3 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass, per 100 parts by mass of the total amount of monomers in the dental composition.
• the content of monomer (a) having an acidic group is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, even more preferably 0.5 mass% or more, and particularly preferably 1 mass% or more, of the total amount (100 mass%) of the dental composition.
• the content of the monomer (a) having an acidic group is preferably 25 mass % or less, more preferably 20 mass % or less, even more preferably 15 mass % or less, and particularly preferably 10 mass % or less, of the total amount (100 mass %) of the dental composition.
• Examples of the monomer (b) having no acidic group in the present invention include a hydrophobic monomer (b-1) having no acidic group and having a solubility in water at 25° C. of less than 10% by mass (hereinafter, may be simply referred to as "hydrophobic monomer (b-1)”); and a hydrophilic monomer (b-2) having no acidic group and having a solubility in water at 25° C. of 10% by mass or more (hereinafter, may be simply referred to as "hydrophilic monomer (b-2)").
• the monomer (b) having no acidic group may be used alone or in combination of two or more kinds.
• Hydrophobic monomer (b-1) having no acidic group The hydrophobic monomer (b-1) having no acidic group improves the handleability of the dental composition and the mechanical strength (flexural strength) of the cured product, and reduces the amount of water absorbed and the amount of dissolution.
• a radically polymerizable monomer having no acidic group and a polymerizable group is preferred, and from the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acryloyloxy group and/or a (meth)acrylamide group.
• the hydrophobic monomer (b-1) means a monomer which does not have an acidic group and has a solubility in water at 25° C.
• hydrophobic monomer (b-1) examples include monofunctional hydrophobic monomers (e.g., (meth)acrylate-based monomers, (meth)acrylamide-based monomers), aromatic compound-based bifunctional hydrophobic monomers, aliphatic compound-based bifunctional hydrophobic monomers, and trifunctional or higher hydrophobic monomers.
• monofunctional hydrophobic monomers e.g., (meth)acrylate-based monomers, (meth)acrylamide-based monomers
• aromatic compound-based bifunctional hydrophobic monomers e.g., (meth)acrylate-based monomers, (meth)acrylamide-based monomers
• aromatic compound-based bifunctional hydrophobic monomers e.g., aliphatic compound-based bifunctional hydrophobic monomers, and trifunctional or higher hydrophobic monomers.
• the hydrophobic monomer (b-1) may be used alone or in combination of two or more kinds.
• the monofunctional hydrophobic monomer examples include aliphatic compound-based monofunctional (meth)acrylate monomers such as n-stearyl methacrylate; aliphatic compound-based monofunctional (meth)acrylate monomers containing an ether bond such as butoxydiethylene glycol methacrylate and methoxypolyethylene glycol methacrylate (average number of moles of oxyethylene groups added: 9); alicyclic compound-based monofunctional (meth)acrylates such as cyclohexyl methacrylate, isobornyl methacrylate, and dicyclopentanyl methacrylate.
• aliphatic compound-based monofunctional (meth)acrylate monomers such as n-stearyl methacrylate
• aliphatic compound-based monofunctional (meth)acrylate monomers containing an ether bond such as butoxydiethylene glycol methacrylate and methoxypolyethylene glycol methacrylate (average number of moles of oxyethylene groups added: 9)
• monofunctional (meth)acrylate monomers having an aromatic ring group such as benzyl methacrylate (commonly known as BEMA), 2-phenoxyethyl methacrylate (commonly known as PEMA), phenoxybenzyl methacrylate (commonly known as POB-MA), 1-naphthylmethyl (meth)acrylate, or 2-naphthylmethyl (meth)acrylate; and (meth)acrylate monomers containing a heterocyclic group (for example, a cyclic ether group, etc.), such as tetrahydrofurfuryl methacrylate (commonly known as "THF-MA").
• BEMA benzyl methacrylate
• PEMA 2-phenoxyethyl methacrylate
• POB-MA phenoxybenzyl methacrylate
• 1-naphthylmethyl (meth)acrylate or 2-naphthylmethyl (meth)acrylate
• the monofunctional (meth)acrylate monomer having an aromatic ring group one having one or two phenyl groups is preferred.
• the (meth)acrylate monomer containing a heterocyclic group one having one or two heterocyclic groups (for example, a cyclic ether group, etc.) is preferable.
• aromatic bifunctional hydrophobic monomer examples include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, and the like.
• 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane commonly known as "Bis-GMA”
• 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane
• 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane are preferred.
• Examples of the aliphatic compound-based bifunctional hydrophobic monomer include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and the like.
• Examples of such compounds include ol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl)di(meth)acrylate, N-methacryloyloxyethyl acrylamide (commonly known as "MAEA"), N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N-(1-ethyl-(2-methacryloyloxy)ethyl)acrylamide, and N-(2-(2-methacryloyloxyethoxy)ethyl)acrylamide.
• MAEA N-methacryloyloxypropyl acrylamide
• N-methacryloyloxybutyl acrylamide N-(1-ethyl-(2-methacryloyloxy)ethyl)acrylamide
• triethylene glycol diacrylate triethylene glycol dimethacrylate (commonly known as "3G")
• neopentyl glycol di(meth)acrylate 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane
• 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl)dimethacrylate commonly known as "UDMA”
• 1,10-decanediol dimethacrylate commonly known as "DD”
• 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl)dimethacrylate are preferred from the viewpoint of mechanical strength and handling.
• 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, UDMA, and DD are preferred.
• adhesion to tooth structure particularly dentin, MAEA and N-methacryloyloxypropylacrylamide are preferred.
• hydrophobic monomers having trifunctionality or higher 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]tetra(meth)acrylate, and 1,7-diacryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxaheptane.
• N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred.
• hydrophobic monomers (b-1) from the viewpoints of mechanical strength (bending strength), water absorption amount, solubility amount and handleability, bifunctional hydrophobic monomers based on aromatic compounds, and bifunctional hydrophobic monomers and monofunctional hydrophobic monomers based on aliphatic compounds are preferably used.
• aromatic bifunctional monomer Bis-GMA and D-2.6E are preferred.
• aliphatic compound-based bifunctional monomer 3G, neopentyl glycol di(meth)acrylate, UDMA, DD, and MAEA are preferred.
• monofunctional hydrophobic monomer 1-naphthylmethyl methacrylate (commonly known as "1-NMMA"), THF-MA, BEMA, POB-MA, and PEMA are preferred.
• hydrophobic monomers (b-1) when used as a dental composition, from the viewpoint of mechanical strength and adhesion to tooth structure, hydrophobic monomers without hydroxyl groups (monofunctional hydrophobic monomers without hydroxyl groups, bifunctional hydrophobic monomers of aromatic compounds without hydroxyl groups, and bifunctional hydrophobic monomers of aliphatic compounds without hydroxyl groups) are preferred, with D-2.6E, DD, UDMA, MAEA, THF-MA, BEMA, POB-MA, and PEMA being more preferred, and D-2.6E, DD, MAEA, and THF-MA being even more preferred.
• the content of the hydrophobic monomer (b-1) in the dental composition is preferably 20 to 98 parts by mass, more preferably 40 to 95 parts by mass, even more preferably 60 to 92 parts by mass, and particularly preferably 60 to 90 parts by mass, per 100 parts by mass of the total amount of the monomers in the dental composition.
• the content of the hydrophobic monomer (b-1) is preferably 5 mass% or more, more preferably 8 mass% or more, even more preferably 10 mass% or more, and particularly preferably 15 mass% or more, of the total amount (100 mass%) of the dental composition, from the viewpoints of adhesion to tooth structure, mechanical strength of the cured product, and handleability.
• the content of the hydrophobic monomer (b-1) is preferably 45 mass % or less, more preferably 40 mass % or less, even more preferably 35 mass % or less, and particularly preferably 30 mass % or less, based on the total amount (100 mass %) of the dental composition.
• Hydrophilic monomer (b-2) having no acidic group The hydrophilic monomer (b-2) can improve the wettability of the self-adhesive dental composite resin to tooth tissue and its permeability into tooth tissue (enamel/dentin), thereby improving the adhesive strength to tooth tissue.
• the hydrophilic monomer (b-2) is preferably a radical polymerizable monomer having no acidic group but a polymerizable group. From the viewpoint of easiness of radical polymerization, the polymerizable group is preferably a (meth)acryloyloxy group and/or a (meth)acrylamide group.
• the hydrophilic monomer (b-2) means a monomer which does not have an acidic group and has a solubility in water at 25° C. of 10% by mass or more, preferably a monomer which has a solubility of 30% by mass or more, and more preferably a monomer which can be dissolved in water at any ratio at 25° C.
• the hydrophilic monomer is preferably one having a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group, or an amide group.
• hydrophilic monomer (b-2) examples include hydrophilic monofunctional (meth)acrylate monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, and polyethylene glycol di(meth)acrylate (average number of moles of oxyethylene groups added: 9 or more); -Hydrophilic monofunctional (meth)acrylamide monomers such as methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, 4-(meth)
• hydrophilic monomers (b-2) from the viewpoint of adhesion to tooth structure, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and hydrophilic monofunctional (meth)acrylamide monomers are preferred, and 2-hydroxyethyl (meth)acrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide are more preferred.
• the hydrophilic monomer (b-2) may be used alone or in combination of two or more kinds.
• the content of the hydrophilic monomer (b-2) in the dental composition is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, further preferably 0 to 30 parts by mass, and particularly preferably 0 to 25 parts by mass, in 100 parts by mass of the total amount of the monomers.
• the content of the hydrophilic monomer (b-2) may be 0 part by mass in 100 parts by mass of the total amount of the monomers.
• a (meth)acrylic compound (b-3) having a weight average molecular weight of 1,000 to 80,000 and a weight average molecular weight per polymerizable group of 1,250 or more and less than 20,000 may be used in the dental composition of the present invention to impart low polymerization shrinkage stress.
• a (meth)acrylic compound having a weight average molecular weight of 1,000 to 80,000 and a weight average molecular weight per polymerizable group of 1,250 or more and less than 20,000 in a monomer (b) having no acidic group is referred to as (meth)acrylic compound (b-3) regardless of its solubility in water at 25°C.
• the (meth)acrylic compound (b-3) can be roughly classified into two types: urethane-modified (meth)acrylic compound (b-3a) and (meth)acrylic compound not having a urethane skeleton (b-3b). From the viewpoints of ease of introduction of the (meth)acrylic group and the effect of reducing polymerization shrinkage stress, the urethane-type (meth)acrylic compound (b-3a) is preferred.
• the urethane-type (meth)acrylic compound (b-3a) can be easily synthesized, for example, by addition reaction of a polyol containing a polymer skeleton described below, a compound having an isocyanate group (-NCO), and a (meth)acrylic compound having a hydroxyl group (-OH).
• the urethane-modified (meth)acrylic compound (b-3a) can be easily synthesized by subjecting a (meth)acrylic compound having a hydroxyl group to a ring-opening addition reaction with a lactone or an alkylene oxide, and then subjecting the resulting compound having a hydroxyl group at one end to an addition reaction with a compound having an isocyanate group.
• the (meth)acrylic compound (b-3b) having no urethane skeleton can be obtained, for example, by subjecting a polymer of a monomer having a hydroxyl group to a dehydration condensation reaction with (meth)acrylic acid.
• the urethanized (meth)acrylic compound (b-3a) is preferably a (meth)acrylate having, in addition to a urethane bond, a structure (polymer skeleton) selected from the group consisting of polyesters, polycarbonates, polyurethanes, polyethers, polyconjugated dienes, and hydrogenated polyconjugated dienes, and more preferably a (meth)acrylate having at least one polyol moiety selected from the group consisting of polyesters, polycarbonates, polyurethanes, polyethers, polyconjugated dienes, and hydrogenated polyconjugated dienes having a structure derived from an aliphatic diol unit having 4 to 18 carbon atoms and a branched structure in one molecule.
• examples of the polyester include copolymers of dicarboxylic acids (aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 18 carbon atoms, copolymers of dicarboxylic acids (saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid) and aliphatic diols having 2 to 18 carbon atoms, polymers of ⁇ -propiolactone, polymers of ⁇ -butyrolactone, polymers of ⁇ -valerolactone, polymers of ⁇ -caprolactone, and copolymers thereof.
• dicarboxylic acids aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid
• copolymers of dicarboxylic acids saturated aliphatic dicarboxylic
• copolymers of dicarboxylic acids aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 12 carbon atoms
• copolymers of dicarboxylic acids saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid
• aliphatic diols having 2 to 12 carbon atoms are preferred.
• polycarbonate examples include polycarbonates derived from an aliphatic diol having 2 to 18 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from an aliphatic diol having 2 to 18 carbon atoms and bisphenol A. Of these, polycarbonates derived from an aliphatic diol having 2 to 12 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from an aliphatic diol having 2 to 12 carbon atoms and bisphenol A are preferred.
• polyurethane examples include polymers of aliphatic diols having 2 to 18 carbon atoms and diisocyanates having 1 to 18 carbon atoms, and polymers of aliphatic diols having 2 to 12 carbon atoms and diisocyanates having 1 to 12 carbon atoms are preferred.
• polyethers include polyethylene glycol, polypropylene glycol, polybutylene glycol, and poly(1-methylbutylene glycol).
• polyconjugated dienes and hydrogenated polyconjugated dienes examples include 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, poly(butadiene-isoprene), poly(butadiene-styrene), poly(isoprene-styrene), polyfarnesene, and hydrogenated products thereof.
• the structures of polyester, polycarbonate, and polyconjugated diene are preferred, and the structures of polyester, polycarbonate, and polyconjugated diene having a structure derived from an aliphatic diol unit having 4 to 18 carbon atoms and a branched structure are more preferred.
• the above-mentioned polyol having a polymer skeleton can be used for the production of the urethane-modified (meth)acrylic compound (b-3a).
• Examples of compounds having an isocyanate group include hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMHMDI), tricyclodecane diisocyanate (TCDDI), and adamantane diisocyanate (ADI).
• HDI hexamethylene diisocyanate
• TDI tolylene diisocyanate
• XDI xylylene diisocyanate
• MDI diphenylmethane diisocyanate
• IPDI isophorone diisocyanate
• THMDI trimethylhexamethylene diisocyanate
• TDDI tricyclodecane diisocyanate
• ADI adamantane diisocyanate
• Examples of (meth)acrylic compounds having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin mono(meth)acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth)acrylate.
• Hydroxy(meth)acrylate compounds such as 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pentaerythritol tri(meth)acrylate, and dipentaerythritol tri- or tetra(meth)acrylate; hydroxy(meth)acrylamide compounds such as N-hydroxyethyl(meth)acrylamide, and N,N-bis(2-hydroxyethyl)(meth)acrylamide.
• Examples of the aliphatic diols having 4 to 18 carbon atoms and a branched structure include 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 2-methyl-1,10-decanediol, 2,9-dimethyl-1,10-decanediol, 2-methyl-1,11-undecanediol, and 2-methyl-1,12-undecanediol.
• dimethyl-1,15-pentadecanediol examples include 2,14-dimethyl-1,15-pentadecanediol, 2,14-dimethyl-1,15-pentadecanediol, 2-methyl-1,16-hexadecanediol, and 2,15-dimethyl-1,16-hexadecanediol.
• an aliphatic diol having 5 to 12 carbon atoms and a methyl group as a side chain such as 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, or 2,8-dimethyl-1,9-nonanediol, as the polyol component, more preferably 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, or 2,7-dimethyl-1,8-octanediol, and even more preferably 3-methyl-1,5-pentanediol or 2-methyl-1,8
• the resulting urethane-modified (meth)acrylic compound (b-3a) may be any combination of reaction products of a polyol having at least one structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene, a compound having an isocyanate group, and a (meth)acrylic compound having a hydroxyl group.
• the (meth)acrylic compound (b-3b) having no urethane skeleton preferably has a structure (polymer skeleton) selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene.
• examples of the polyester include copolymers of dicarboxylic acids (aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 18 carbon atoms, copolymers of dicarboxylic acids (saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid) and aliphatic diols having 2 to 18 carbon atoms, polymers of ⁇ -propiolactone, polymers of ⁇ -butyrolactone, polymers of ⁇ -valerolactone, polymers of ⁇ -caprolactone, and copolymers thereof.
• dicarboxylic acids aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid
• copolymers of dicarboxylic acids saturated aliphatic dicarboxylic
• copolymers of dicarboxylic acids aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid) and aliphatic diols having 2 to 12 carbon atoms
• copolymers of dicarboxylic acids saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid
• aliphatic diols having 2 to 12 carbon atoms are preferred.
• polycarbonate examples include polycarbonates derived from an aliphatic diol having 2 to 18 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from an aliphatic diol having 2 to 18 carbon atoms and bisphenol A. Of these, polycarbonates derived from an aliphatic diol having 2 to 12 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from an aliphatic diol having 2 to 12 carbon atoms and bisphenol A are preferred.
• polyurethane examples include polymers of aliphatic diols having 2 to 18 carbon atoms and diisocyanates having 1 to 18 carbon atoms, and polymers of aliphatic diols having 2 to 12 carbon atoms and diisocyanates having 1 to 12 carbon atoms are preferred.
• polyethers include polyethylene glycol, polypropylene glycol, polybutylene glycol, and poly(1-methylbutylene glycol).
• polyconjugated dienes and hydrogenated polyconjugated dienes examples include 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, poly(butadiene-isoprene), poly(butadiene-styrene), poly(isoprene-styrene), polyfarnesene, and hydrogenated products thereof.
• the structures of polyester, polycarbonate, and polyconjugated diene are preferred in terms of excellent flexibility and water resistance.
• the above-mentioned polyol having a polymer skeleton can be used.
• the glass transition temperature and acetone solubility of the (meth)acrylic compound (b-3b) having no urethane skeleton can be adjusted.
• the obtained (meth)acrylic compound (b-3b) not having a urethane skeleton may be a reaction product of any combination of the above-mentioned polyol having at least one structure selected from the group consisting of polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene, and a (meth)acrylic compound having a hydroxyl group.
• the polyester, polycarbonate, polyurethane, polyether, polyconjugated diene, and hydrogenated polyconjugated diene, and the (meth)acrylic compound having a hydroxyl group include those exemplified as the urethane-modified (meth)acrylic compound (b-3a).
• the weight average molecular weight (Mw) of the (meth)acrylic compound (b-3) is preferably from 1,000 to 80,000, more preferably from 2,000 to 50,000, and even more preferably from 3,000 to 20,000, from the viewpoint of viscosity and the effect of reducing polymerization shrinkage stress.
• the weight average molecular weight (Mw) means a weight average molecular weight calculated in terms of polystyrene, determined by gel permeation chromatography (GPC).
• the weight average molecular weight per (meth)acrylic group in the (meth)acrylic compound (b-3) is preferably 1,250 or more and less than 20,000, more preferably 1,500 or more and 17,500 or less, even more preferably 1,800 or more and 16,000 or less, and particularly preferably 2,500 or more and 15,000 or less.
• the relationship between the number of polymerizable groups and the weight average molecular weight of the (meth)acrylic compound (b-3a) is within the above range, appropriate crosslinking occurs, making it possible to more effectively maintain mechanical strength while suppressing polymerization shrinkage stress.
• the (meth)acrylic compound (b-3) contains a polymerizable group other than the (meth)acrylic group, such as a vinyl group or a styrene group, the polymerization shrinkage stress may become large depending on the polymerization form. Therefore, the number of polymerizable groups other than the (meth)acrylic group in the (meth)acrylic compound (b-3) is preferably 2 or less, and more preferably 0.
• the polarity difference between the (meth)acrylic compound (b-3) and other monomer components is important, and it is preferable that the (meth)acrylic compound (b-3) has low solubility in acetone compared to other monomers that have high solubility in acetone.
• the solubility of the (meth)acrylic compound (b-3) in acetone is preferably less than 50 g/L, more preferably less than 30 g/L, even more preferably less than 25 g/L, particularly preferably less than 20 g/L, and most preferably less than 10 g/L.
• the viscosity of the (meth)acrylic compound (b-3) at 25°C is preferably 1,000 to 10,000,000 mPa ⁇ s, more preferably 5,000 to 7,500,000 mPa ⁇ s, and even more preferably 10,000 to 7,000,000 mPa ⁇ s, from the viewpoints of operability and the effect of reducing polymerization shrinkage stress.
• this viscosity refers to the viscosity measured at 25°C using a Brookfield rotational viscometer. Measurement conditions such as time and rotation speed are appropriately adjusted depending on the viscosity range.
• (meth)acrylic compound (b-3) commercially available products may be used.
• commercially available products include urethane polymers having a polymerizable group at the end, such as the "Art Resin” series (UN7600, UN7700) manufactured by Negami Chemical Industrial Co., Ltd., and the "Kuraray” series (LIR-30, LIR-50, LIR-390, LIR-403, LIR-410, UC-102M, UC-203M, LIR-700, LIR-800, LIR-900, LIR-1000, LIR-1100, LIR-1200, LIR-1300, LIR-1400, LIR-1500, LIR-1600, LIR-1700, LIR-1800, LIR-1900, LIR-2000, LIR-2100, LIR-2200, LIR-2300, LIR-2400, LIR-2500, LIR-2600, LIR-2700, LIR-2800, LIR-2900, LIR-3000, LIR-3200, LIR-3300, LIR-3400, L
• liquid polybutadiene "NISSO-PB" (B-1000, B-2000, B-3000, BI-2000, BI-3000, G-1000, G-2000, G-3000, GI-1000, GI-2000, GI-3000, TEAI-1000, TE-2000, TE-4000, JP-100, JP-200) manufactured by Nippon Soda Co., Ltd., and the like.
• the content of the (meth)acrylic compound (b-3) in the dental composition of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass, even more preferably 1 to 35 parts by mass, and particularly preferably 5 to 25 parts by mass, from the viewpoints of mechanical strength, paste properties, and the effect of reducing polymerization shrinkage stress, per 100 parts by mass of the total amount of monomers.
• the content of the (meth)acrylic compound (b-3) is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 1 mass % or more, and particularly preferably 1.5 mass % or more, based on the total amount of the dental composition (100 mass %).
• the content of the (meth)acrylic compound (b-3) is preferably 30 mass % or less, more preferably 25 mass % or less, even more preferably 20 mass % or less, and particularly preferably 15 mass % or less, based on 100 mass % of the total amount of the dental composition.
• the total content of the monomer (b) not having an acidic group in the dental composition is preferably 60 to 99 parts by mass, more preferably 65 to 97.5 parts by mass, even more preferably 70 to 95 parts by mass, and particularly preferably 75 to 95 parts by mass, per 100 parts by mass of the total amount of the monomers, from the viewpoints of the properties, mechanical strength, adhesion to tooth substance, and mechanical strength of the dental composition.
• the dental composition of the present invention contains a polymerization initiator (c) for hardening the monomer.
• a polymerization initiator (c) for hardening the monomer.
• a photopolymerization initiator (c-1) or a chemical polymerization initiator (c-2) can be used. Each of them may be used alone or in combination of two or more kinds.
• the photopolymerization initiator (c-1) is classified into a water-soluble photopolymerization initiator (c-1a) and a water-insoluble photopolymerization initiator (c-1b).
• a water-soluble photopolymerization initiator (c-1a) may be used, or only the water-insoluble photopolymerization initiator (c-1b) may be used.
• the water-soluble photopolymerization initiator (c-1a) and the water-insoluble photopolymerization initiator (c-1b) may be used in combination, and it is preferable to use them in combination.
• the water-soluble photopolymerization initiator (c-1a) improves the polymerization hardening property at the hydrophilic tooth surface interface, and can realize high adhesive strength.
• the water-soluble photopolymerization initiator (c-1a) has a solubility in water at 25° C. of 10 g/L or more, preferably 15 g/L or more, more preferably 20 g/L or more, and even more preferably 25 g/L or more. When the solubility is 10 g/L or more, the water-soluble photopolymerization initiator (c-1a) dissolves sufficiently in water in the tooth substance at the adhesive interface, and the polymerization promoting effect is easily exhibited.
• water-soluble photopolymerization initiator (c-1a) examples include water-soluble thioxanthones; water-soluble acylphosphine oxides; 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one having a (poly)ethylene glycol chain introduced to a hydroxyl group and/or a phenyl group of 1-hydroxycyclohexyl phenyl ketone having a (poly)ethylene glycol chain introduced to a hydroxyl group and/or a phenyl group of 1-hydroxycyclohexyl phenyl ketone having -OCH 2 COO - Na + introduced to a phenyl group of 1-hydroxycyclohexyl phenyl ketone; 2-hydroxy-2-methyl-1-phenylpropan-1-one having a (poly)ethylene glycol chain introduced to a hydroxyl group and/or a phenyl group of 2-hydroxy-2-methyl-1-phenyl
• ⁇ -aminoalkylphenones such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-(dimethylamino)-1-[(4-morpholino)phenyl]-1-butanone in which the amino group is converted into a quaternary ammonium salt.
• water-soluble thioxanthones examples include 2-hydroxy-3-(9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(1-methyl-9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2 -Hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-di
• the water-soluble acylphosphine oxides include acylphosphine oxides represented by the following general formula (1), (2) or (3).
• R 1 to R 9 and R 11 to R 16 are each independently a C 1 to C 4 linear or branched alkyl group or a halogen atom;
• M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or an ammonium ion represented by HN + R 17 R 18 R 19 (wherein R 17 , R 18 , and R 19 are each independently an organic group or a hydrogen atom);
• n is 1 or 2;
• X is a C 1 to C 4 linear or branched alkylene group;
• R 10 is represented by —CH(CH 3 )COO(C 2 H 4 O) p CH 3 , where p is an integer from 1 to 1,000.
• the alkyl group of R 1 to R 9 and R 11 to R 16 is not particularly limited as long as it is a C 1 to C 4 linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a 2-methylpropyl group, and a tert-butyl group.
• the alkyl group of R 1 to R 9 and R 11 to R 16 is preferably a C 1 to C 3 linear alkyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
• Examples of X include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, etc.
• X is preferably a C 1 to C 3 linear alkylene group, more preferably a methylene group or an ethylene group, and further preferably a methylene group.
• examples of the substituent on the pyridine ring include halogen atoms (fluorine, chlorine, bromine, and iodine atoms), carboxyl groups, C2 - C6 linear or branched acyl groups, C1 - C6 linear or branched alkyl groups, and C1 - C6 linear or branched alkoxy groups.
• M is preferably an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or an ammonium ion represented by HN + R17R18R19 (wherein the symbols have the same meanings as above).
• the alkali metal ion include a lithium ion, a sodium ion , a potassium ion, a rubidium ion, and a cesium ion.
• Examples of the alkaline earth metal ion include a calcium ion, a strontium ion, a barium ion, and a radium ion.
• the organic groups of R 17 , R 18 and R 19 include the same groups as the substituents of the pyridine ring (excluding halogen atoms).
• compounds represented by general formula (1) in which R 1 to R 3 are all methyl groups, compounds represented by general formula (2) in which R 4 to R 9 are all methyl groups, and compounds represented by general formula (3) in which R 11 to R 16 are all methyl groups are particularly preferred in terms of adhesion to tooth structure.
• ammonium ions include ammonium ions derived from various amines.
• amines include ammonia, trimethylamine, diethylamine, dimethylaniline, ethylenediamine, triethanolamine, N,N-dimethylamino methacrylate, 4-(N,N-dimethylamino)benzoic acid and its alkyl esters, 4-(N,N-diethylamino)benzoic acid and its alkyl esters, and N,N-bis(2-hydroxyethyl)-p-toluidine.
• p is 1 or more, preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
• p is 1000 or less, preferably 100 or less, more preferably 75 or less, and even more preferably 50 or less, from the viewpoint of adhesiveness.
• Water-soluble acylphosphine oxides having such a structure can be synthesized according to known methods, and some of them are also available as commercially available products. For example, they can be synthesized by the methods disclosed in JP-A-57-197289 and WO 2014/095724.
• the water-soluble photopolymerization initiator (c-1a) may be used alone or in combination of two or more kinds.
• the water-soluble photopolymerization initiator (c-1a) may be dissolved in the dental composition or may be dispersed in the dental composition in powder form.
• the average particle size is preferably 500 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less.
• the average particle size is preferably 0.01 ⁇ m or more.
• the average particle size of the water-soluble photopolymerization initiator (c-1a) is preferably in the range of 0.01 to 500 ⁇ m, more preferably in the range of 0.01 to 100 ⁇ m, and even more preferably in the range of 0.01 to 50 ⁇ m.
• the average particle size of each water-soluble photopolymerization initiator (c-1a) powder can be calculated as the volume average particle size after performing image analysis using image analysis particle size distribution measurement software (Mac-View; manufactured by Mountec Co., Ltd.) based on electron micrographs of 100 or more particles.
• image analysis particle size distribution measurement software Mac-View; manufactured by Mountec Co., Ltd.
• the shape of the initiator may be, but is not particularly limited to, various shapes such as spherical, needle-like, plate-like, and crushed.
• the water-soluble photopolymerization initiator (c-1a) can be prepared by conventional methods such as the pulverization method, freeze-drying method, and reprecipitation method, and from the viewpoint of the average particle size of the obtained powder, the freeze-drying method and the reprecipitation method are preferred, and the freeze-drying method is more preferred.
• the content of the water-soluble photopolymerization initiator (c-1a) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the monomers in the dental composition, and from the viewpoint of superior adhesion to tooth structure, the content is more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass.
• the content of the water-soluble photopolymerization initiator (c-1a) is equal to or more than the lower limit, polymerization at the adhesion interface proceeds sufficiently, and sufficient adhesive strength is easily obtained.
• the content of the water-soluble photopolymerization initiator (c-1a) is equal to or less than the upper limit, sufficient adhesive strength is easily obtained.
• Non-water-soluble photopolymerization initiator (c-1b) The dental composition preferably contains a water-insoluble photopolymerization initiator (c-1b) having a solubility in water at 25° C. of less than 10 g/L (hereinafter, may be referred to as water-insoluble photopolymerization initiator (c-1b)).
• the dental composition may contain only the water-insoluble photopolymerization initiator (c-1b), but from the viewpoint of curability and mechanical strength, it is preferable to contain a water-insoluble photopolymerization initiator (c-1b) having a solubility in water at 25° C. of less than 10 g/L in addition to the water-soluble photopolymerization initiator (c-1a).
• the water-insoluble photopolymerization initiator (c-1b) used in the present invention can be a known photopolymerization initiator.
• the water-insoluble photopolymerization initiator (c-1b) may be blended alone or in combination of two or more kinds.
• non-water-soluble photopolymerization initiator (c-1b) examples include (bis)acylphosphine oxides, thioxanthones, ketals, ⁇ -diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, ⁇ -aminoketone compounds, etc., other than the water-soluble photopolymerization initiator (c-1a).
• examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, and benzoyldi(2,6-dimethylphenyl)phosphonate.
• bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphos
• thioxanthones examples include thioxanthone and 2-chlorothioxanthen-9-one.
• ketals examples include benzyl dimethyl ketal and benzyl diethyl ketal.
• ⁇ -diketones examples include diacetyl, benzil, dl-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzil, and acenaphthenequinone.
• dl-camphorquinone is particularly preferred because it has a maximum absorption wavelength in the visible light region.
• the coumarins include, for example, 3,3'-carbonylbis(7-diethylaminocoumarin), 3-(4-methoxybenzoyl)coumarin, 3-thienoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p-nitrobenzoyl)coumarin, 3,5-carbonylbis(7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3'-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo[f]coumarin, and 3-carboxycoumarin.
• 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are particularly suitable.
• anthraquinones examples include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, and 1-hydroxyanthraquinone.
• benzoin alkyl ether compounds examples include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
• Examples of the ⁇ -aminoketone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.
• water-insoluble photopolymerization initiators (c-1b) it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides, ⁇ -diketones, and coumarins. This results in a dental composition that has excellent photocurability in the visible and near-ultraviolet regions and exhibits sufficient photocurability whether a halogen lamp, light-emitting diode (LED), or xenon lamp is used as a light source.
• a halogen lamp, light-emitting diode (LED), or xenon lamp is used as a light source.
• the content of the water-insoluble photopolymerization initiator (c-1b) is not particularly limited, but from the viewpoint of the curability of the resulting dental composition, the content is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of the monomers in the dental composition.
• the content of the water-insoluble photopolymerization initiator (c-1b) equal to or less than the upper limit, even when the polymerization performance of the water-insoluble photopolymerization initiator (c-1b) itself is low, sufficient adhesive strength is easily obtained, and further, precipitation of the water-insoluble photopolymerization initiator (c-1b) itself from the dental composition can be suppressed.
• the mass ratio of the water-soluble photopolymerization initiator (c-1a) to the water-insoluble photopolymerization initiator (c-1b) in the present invention is preferably 10:1 to 1:10, more preferably 7:1 to 1:7, even more preferably 5:1 to 1:5, and particularly preferably 3:1 to 1:3.
• the water-soluble photopolymerization initiator (c-1a) When the water-soluble photopolymerization initiator (c-1a) is contained in a mass ratio of more than 10:1, the hardening property of the dental composition itself is reduced, and the adhesive strength to tooth structure and bending strength are reduced, so that it may become difficult to achieve the effects of the present invention.
• the water-insoluble photopolymerization initiator (c-1b) when the water-insoluble photopolymerization initiator (c-1b) is contained in a mass ratio of more than 1:10, the hardening property of the dental composition itself is enhanced, but the promotion of polymerization at the adhesive interface becomes insufficient, and it may become difficult to achieve high adhesive strength.
• the dental composition may further contain a chemical polymerization initiator (c-2), and an organic peroxide is preferably used.
• the organic peroxide used in the above-mentioned chemical polymerization initiator (c-2) is not particularly limited, and known organic peroxides can be used.
• Representative organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates. Specific examples of these organic peroxides include those described in International Publication No. 2008/087977.
• the chemical polymerization initiator may be used alone or in combination of two or more kinds.
• the dental composition contains a filler (d) in order to adjust the handleability, increase the mechanical strength (flexural strength, etc.) of the cured product, and increase the adhesion to tooth structure.
• a filler (d) examples include inorganic fillers, organic-inorganic composite fillers, organic fillers, etc.
• the filler (d) may be used alone or in combination of two or more kinds.
• the material for the inorganic filler it is preferable to use various glasses (containing silica as the main component (containing 5% by mass or more of silica, preferably 10% by mass or more of silica), and, as necessary, oxides of heavy metals, boron, aluminum, etc.).
• various glasses containing silica as the main component (containing 5% by mass or more of silica, preferably 10% by mass or more of silica), and, as necessary, oxides of heavy metals, boron, aluminum, etc.).
• inorganic fillers include glass powders of general compositions such as fused silica, quartz, soda lime silica glass, E glass, C glass, and borosilicate glass (Pyrex (registered trademark) glass); barium glass, strontium borosilicate glass, lanthanum glass ceramics, fluoroaluminosilicate glass, various ceramics, alumina, silica-titania, silica-zirconia, ytterbium oxide, silica-coated ytterbium fluoride, aluminosilicate glass, barium boroaluminosilicate glass, calcium fluoroaluminosilicate glass, and the like.
• glass powders of general compositions such as fused silica, quartz, soda lime silica glass, E glass, C glass, and borosilicate glass (Pyrex (registered trademark) glass)
• the inorganic silicate examples include composite oxides such as strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass; diatomaceous earth, kaolin, clay minerals (such as montmorillonite); activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, yttrium fluoride, calcium phosphate, barium sulfate, zirconium oxide, titanium oxide, and hydroxyapatite. These may be used alone or in combination of two or more.
• composite oxides such as strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass
• diatomaceous earth such as montmorillonite
• clay minerals such as montmorillonite
• activated clay synthetic zeolite
• mica calcium fluoride
• inorganic fillers containing, as constituent elements, metal elements such as aluminum, strontium, zirconium, barium, lanthanum, ytterbium, titanium, and bismuth, which have high X-ray contrast properties, are preferred (for example, barium glass, alumina, silica-titania, silica-zirconia, and silica-coated ytterbium fluoride).
• the inorganic filler can be used as an inorganic filler having a relatively high refractive index. These may also be used alone or in combination of two or more.
• quartz, silica, silica-titania, silica-zirconia, barium glass, ytterbium oxide, and silica-coated ytterbium fluoride are preferred, and quartz, silica, silica-titania, silica-zirconia, barium glass, and silica-coated ytterbium fluoride are more preferred, in terms of excellent mechanical strength and transparency of the resulting cured product.
• silica-zirconia, barium glass, and silica-coated ytterbium fluoride are preferred, with silica-zirconia and barium glass being particularly preferred.
• the inorganic filler used may be a commercially available product.
• examples of commercially available products include silica such as Aerosil (registered trademark) 90, Aerosil (registered trademark) 130, Aerosil (registered trademark) 150, Aerosil (registered trademark) 200, Aerosil (registered trademark) 255, Aerosil (registered trademark) 300, Aerosil (registered trademark) 380, Aerosil (registered trademark) OX50, and Aerosil (registered trademark) R972 (all manufactured by Nippon Aerosil Co., Ltd.); barium glass such as GM27884, 8235 (manufactured by Schott), product code "E-3000” (manufactured by Estech), strontium borosilicate glass (E-4000, manufactured by ESSTECH), lanthanum glass ceramics (GM31684, manufactured by Schott), and fluoroaluminosilicate glass (GM35429, G018-091, G0
• the inorganic filler may be amorphous, crystalline, or a mixture of both, but it is preferable that it contains at least an amorphous portion.
• the shape of the inorganic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used.
• Examples include irregular fillers (crushed fillers) and spherical fillers.
• an irregular filler as the inorganic filler, and from the viewpoint of handleability, it is preferable to use a spherical filler.
• a spherical filler is a filler in which the particles observed within a unit field of view when a photograph of the filler is taken with an electron microscope are rounded, and the average uniformity obtained by dividing the particle diameter in the direction perpendicular to the maximum diameter by the maximum diameter is 0.6 or more.
• the inorganic filler is preferably surface-treated in advance with a known surface treatment agent such as a silane coupling agent in order to adjust the mechanical strength and fluidity of the cured product.
• a known surface treatment agent such as a silane coupling agent
• an inorganic filler with the hydroxyl groups surface-treated can be obtained.
• Surface treatment agents include, for example, silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri( ⁇ -methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, and ⁇ -aminopropyltriethoxysilane, with vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, and ⁇ -amino
• the surface treatment method can be any known method without any particular limitation, and examples of such methods include a method in which the surface treatment agent is sprayed onto the inorganic filler while vigorously stirring the inorganic filler, a method in which the inorganic filler and the surface treatment agent are dispersed or dissolved in a suitable solvent and then the solvent is removed, and a method in which the alkoxy groups of the surface treatment agent are hydrolyzed in an aqueous solution with an acid catalyst to convert them to silanol groups, which are then attached to the inorganic filler surface in the aqueous solution, and then the water is removed.
• the reaction between the inorganic filler surface and the surface treatment agent can be completed by heating in the range of usually 50 to 150° C., thereby performing the surface treatment.
• the amount of the surface treatment is not particularly limited, and for example, 0.1 to 40 parts by mass of the surface treatment agent can be used per 100 parts by mass of the inorganic filler before treatment.
• the organic-inorganic composite filler is obtained by adding a monomer to the above-mentioned inorganic filler in advance, forming it into a paste, polymerizing it, and pulverizing it.
• the organic-inorganic composite filler means a filler containing an inorganic filler and a polymer of a monomer.
• the organic-inorganic composite filler may be a filler obtained by mixing Bis-GMA, 3G, and a surface-treated silica filler, polymerizing the mixture, and then pulverizing the mixture.
• the shape of the organic-inorganic composite filler is not particularly limited, and the particle size of the filler may be appropriately selected.
• the organic-inorganic composite filler may also be used alone or in combination of two or more kinds, and the organic-inorganic composite filler is also preferably surface-treated from the viewpoint of mechanical strength. Examples and preferred types of surface treatment agents are the same as those for the inorganic filler. From the viewpoint of the handling property and mechanical strength of the obtained dental composition, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 ⁇ m, more preferably 0.001 to 20 ⁇ m, and even more preferably 0.005 to 15 ⁇ m.
• organic filler material examples include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like. These may be used alone or as a mixture of two or more.
• the shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected. From the viewpoints of the handleability and mechanical strength of the resulting dental composition, the average particle size of the organic filler is preferably 0.001 to 50 ⁇ m, more preferably 0.001 to 20 ⁇ m, and even more preferably 0.005 to 15 ⁇ m.
• the average particle size of the filler can be determined by a laser diffraction scattering method or by observing the particles with an electron microscope.
• the laser diffraction scattering method is convenient for measuring particle sizes of 0.1 ⁇ m or more, and electron microscope observation is convenient for measuring the particle size of ultrafine particles less than 0.1 ⁇ m.
• 0.1 ⁇ m is a measurement value obtained by the laser diffraction scattering method.
• particles formed by agglomeration of primary particles such as aggregated particles
• the average particle size of the filler is the average particle size of the secondary particles, which has a larger particle size, except when the average particle size of the primary particles is clearly stated.
• the laser diffraction scattering method can be performed, for example, using a laser diffraction particle size distribution analyzer (SALD-2300: manufactured by Shimadzu Corporation) to measure on a volume basis using a 0.2% aqueous solution of sodium hexametaphosphate as the dispersion medium.
• SALD-2300 manufactured by Shimadzu Corporation
• electron microscope observation can be performed by taking a photograph of the particles with an electron microscope (S-4000 model, manufactured by Hitachi, Ltd.) and measuring the particle diameters of the particles (200 or more) observed within a unit field of view of the photograph using image analysis particle size distribution measurement software (Mac-View, manufactured by Mountec Co., Ltd.).
• the particle diameter is found as the arithmetic mean of the longest and shortest lengths of the particles, and the average particle diameter is calculated from the number of particles and their particle diameters.
• the refractive index of the filler (d) is not particularly limited, and may be, for example, 1.35 or more and 2.00 or less.
• the refractive index of the filler (d) is preferably 1.40 or more and 1.70 or less, more preferably 1.45 or more and 1.65 or less, and even more preferably 1.50 or more and 1.60 or less.
• the refractive index of the measurement object can be measured by an Abbe refractometer.
• the difference in refractive index between the plurality of fillers is preferably 0.02 or more, more preferably 0.03 or more, and even more preferably 0.04 or more. Since good color compatibility with both enamel and dentin, which have significantly different color tones, is easily obtained, the refractive index difference between multiple fillers is preferably less than 0.10, more preferably 0.09 or less, and even more preferably 0.08 or less.
• the dental composition contains an aggregated filler (d-1) formed by agglomeration of primary particles, from the viewpoints of adjusting the handling property, and having high mechanical strength, excellent polishability, and good paste properties as well as high adhesive strength to tooth structure.
• examples of such fillers include inorganic fillers.
• the primary particles constituting the aggregated filler (d-1) are metal oxides.
• the aggregated filler (d-1) means secondary particles formed by welding primary particles together.
• the aggregated filler (d-1) may be used alone or in combination of two or more kinds.
• metal oxides can be used as the material of the aggregated filler (d-1), among the above-listed materials for the inorganic filler.
• the metal element contained in the metal oxide include metal elements such as boron, silicon, aluminum, strontium, zirconium, barium, lanthanum, ytterbium, titanium, and bismuth. Silicon, aluminum, strontium, zirconium, and barium are preferred, silicon, aluminum, zirconium, and barium are more preferred, silicon and/or zirconium are even more preferred, and silicon and zirconium are particularly preferred.
• the metal elements may be used alone or in combination of two or more kinds. In this specification, boron and silicon are included in the metallic elements.
• the metal oxides also include composite oxides such as silica-titania and silica-zirconia.
• the average particle size of the aggregated filler (d-1) (secondary particles) is preferably 1 to 20 ⁇ m, more preferably 1.5 to 15 ⁇ m, even more preferably 2 to 12.5 ⁇ m, and most preferably 3 to 10 ⁇ m.
• the average particle size of the agglomerated filler (d-1) means the average particle size before the surface treatment.
• the average particle size of the primary particles constituting the aggregated filler (d-1) is preferably 30 to 500 nm, more preferably 40 to 400 nm, even more preferably 50 to 300 nm, and particularly preferably 60 to 200 nm.
• the average particle size of the primary particles constituting the aggregated filler (d-1) means the average particle size before the surface treatment.
• the average particle size of the primary particles may be within a desired range by purchasing a filler (commercially available product) as the raw filler, or by pulverizing the raw filler to obtain a filler having an average particle size of the primary particles within the desired range. Furthermore, the filler may be made to have an average primary particle size within the desired range by classification or the like.
• the specific surface area of the aggregated filler (d-1) measured by the BET method is 5 m 2 /g or more and 60 m 2 /g or less, preferably 8 m 2 /g or more and less than 50 m 2 /g, more preferably 10 m 2 /g or more and 40 m 2 /g or less, even more preferably 12 m 2 /g or more and 35 m 2 /g or less, and particularly preferably 15 m 2 /g or more and 30 m 2 /g or less.
• the specific surface area of the aggregated filler (d-1) means the specific surface area of the secondary particles.
• the method for producing the aggregated filler (d-1) is not particularly limited, and any known method can be used.
• a method for producing the agglomerated filler (d-1) for example, primary particles of the raw metal oxide are pulverized as necessary to obtain a desired average particle size, and then dispersed in a solvent containing a binder to prepare a slurry. The slurry is then spray-dried and granulated. The resulting particles are then heat-treated to obtain the agglomerated filler (d-1) having a desired specific surface area.
• the method of dispersion treatment is not particularly limited, and any known method can be used, such as ultrasonic dispersion.
• the heat treatment is not particularly limited as long as it can adjust the specific surface area to a desired value and can weld the particles, but is preferably performed at 200° C. or higher and 1000° C. or lower, more preferably 300° C. or higher and 950° C. or lower, and even more preferably 350° C. or higher and 900° C. or lower.
• a surface treatment may be further carried out to produce the aggregated filler (d-1).
• the surface treatment is as described above.
• the specific surface area of the aggregated filler (d-1) can be measured by a BET (Brunauer Emmett Teller) multipoint method.
• the method for measuring the specific surface area is as described in the Examples below. It is preferable to measure the specific surface area of the aggregated filler (d-1) in a state where it is not subjected to a surface treatment.
• the measurement results can be analyzed by a multipoint BET method using five points on the adsorption side isotherm where the ratio (P/P) of the adsorption equilibrium pressure P (kPa) to the saturated vapor pressure P (kPa) is in the range of 0.05 to 0.3.
• the inorganic filler used as the aggregate filler (d-1) may be a commercially available product.
• Examples of commercially available products include SG-SZ200G151CMP8, SG-SZ50G151CMP8, and SG-SZ200G154CMP8 (manufactured by Sukgyung AT).
• the content of the aggregated filler (d-1) is 20 to 85 mass% of the total amount (100 mass%) of the dental composition, preferably 30 to 80 mass%, more preferably 35 to 75 mass%, even more preferably 40 to 75 mass%, and particularly preferably 45 to 75 mass%.
• the dental composition preferably contains a filler (d-2) other than the aggregated filler (d-1) (hereinafter, sometimes simply referred to as "filler (d-2)").
• a filler (d-2) other than the aggregated filler (d-1)
• the filler (d-2) include inorganic fillers, organic-inorganic composite fillers, organic fillers, etc.
• the filler (d-2) may be used alone or in combination of two or more kinds.
• the average particle size of the inorganic filler (d-2) other than the aggregated filler (d-1) is preferably 0.001 to 50 ⁇ m, more preferably 0.001 to 20 ⁇ m, and even more preferably 0.005 to 10 ⁇ m.
• the average particle size of the filler (d-2) means the average particle size before the surface treatment.
• a preferred embodiment of the dental composition includes a dental composition in which the filler (d-2) is an inorganic filler.
• the content of the filler (d-2) other than the aggregated filler (d-1) is preferably 0 to 50 mass%, more preferably 1 to 45 mass%, and even more preferably 2 to 40 mass%, based on 100 mass% of the dental composition.
• filler (d-2) other than the aggregated filler (d-1) may not be included.
• the amount of filler (d) is not particularly limited, but from the viewpoints of handling, ease of polishing, mechanical strength of the cured product, and adhesion to tooth structure, it is preferably 50 to 90% by mass, more preferably 55 to 85% by mass, even more preferably 60 to 80% by mass, and particularly preferably 60 to 78% by mass, based on 100% by mass of the dental composition.
• the dental composition contains a polymerization accelerator (e) in addition to the water-soluble photopolymerization initiator (c-1a), the water-insoluble photopolymerization initiator (c-1b), and the chemical polymerization initiator (c-2).
• the polymerization accelerator (e) used in the present invention includes, for example, amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites, thiourea compounds, etc.
• One type of polymerization accelerator (e) may be used alone, or two or more types may be used in combination.
• Amines used as the polymerization accelerator (e) are divided into aliphatic amines and aromatic amines.
• aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; and tertiary aliphatic amines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, and
• aromatic amines include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl- Examples of the benzoic acid
• sulfinic acids and their salts include those described in WO 2008/087977.
• the content of the polymerization accelerator (e) used in the present invention is not particularly limited, but from the viewpoint of the hardening property of the resulting dental composition, it is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of monomers in the dental composition.
• the content of the polymerization accelerator (e) is equal to or greater than the lower limit, polymerization proceeds sufficiently and sufficient adhesive strength is easily obtained.
• the content of the polymerization accelerator (e) is equal to or less than the upper limit, sufficient adhesiveness is easily obtained, and precipitation of the polymerization accelerator (e) itself from the dental composition can be suppressed.
• the dental composition may further contain a fluoride ion-releasing substance.
• a dental composition capable of imparting acid resistance to tooth structure can be obtained.
• fluoride ion releasing substances include fluoride ion releasing polymers such as copolymers of methyl methacrylate and methacrylic acid fluoride; and metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride.
• the above fluoride ion releasing substances may be used alone or in combination of two or more kinds.
• the dental composition may contain known additives within the range that does not impair the performance.
• additives include polymerization inhibitors, antioxidants, colorants (pigments, dyes), ultraviolet absorbers, fluorescent agents, solvents such as organic solvents, thickeners, etc.
• the additives may be used alone or in combination of two or more.
• the content of a solvent (e.g., water, organic solvent) in the dental composition is preferably less than 1 mass %, more preferably less than 0.1 mass %, and even more preferably less than 0.01 mass %, based on a total amount (100 mass %) of the dental composition.
• the dental composition of the present invention preferably contains a polymerization inhibitor.
• the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, 3,5-di-t-butyl-4-hydroxytoluene, etc. These may be used alone or in combination of two or more.
• the content of the polymerization inhibitor is preferably 0.001 to 1.0 part by mass per 100 parts by mass of the total amount of monomers in the dental composition.
• the dental composition of the present invention preferably contains an ultraviolet absorber from the viewpoint of photostability against environmental light such as fluorescent lamps and LEDs, and from the viewpoint of suppressing discoloration of the cured product.
• the ultraviolet absorber include benzotriazole compounds such as 2-(2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-ethylphenyl)benzotriazole, 2-(2-hydroxy-5-propylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, and 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole (Tinuvin 326), and benzimidazole compounds, with Tinuvin 326 being preferred. These may be used alone or in combination of two or more.
• the dental composition of the present invention preferably contains a fluorescent agent from the aesthetic viewpoint of reproducing a color tone close to that of tooth tissue.
• a fluorescent agent from the aesthetic viewpoint of reproducing a color tone close to that of tooth tissue.
• Any known fluorescent agent can be used without any restrictions, but phthalate ester-based fluorescent agents are preferred.
• phthalate ester fluorescent agents include dimethyl 2,5-dihydroxyterephthalate, diethyl 2,5-dihydroxyterephthalate, dimethylaminoterephthalate, and diethylaminoterephthalate. Of these, phthalate ester fluorescent agents substituted with a hydroxyl group, such as diethyl 2,5-dihydroxyterephthalate, are more preferred.
• the fluorescent agent may be used alone or in combination of two or more kinds.
• the content of the fluorescent agent is not particularly limited, but a certain amount is necessary to ensure fluorescence, and conversely, if the content is too high, it tends to become difficult to ensure photostability.
• the content of the fluorescent agent is preferably 0.005 to 0.5 parts by mass, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the total amount of monomers in the dental composition.
• the dental composition of the present invention preferably contains a colorant to reproduce a color tone close to that of tooth structure.
• a colorant to reproduce a color tone close to that of tooth structure.
• the colorant may be used alone or in combination of two or more types.
• a colorant is a component that is added in small amounts to a dental composition.
• the content of one type of colorant is less than 1.0% by mass out of a total of 100% by mass of the dental composition.
• the colorant used may have a refractive index of more than 2.00.
• the refractive index of the colorant may be 2.05 or more, or 2.10 or more.
• the shape of the colorant is not particularly limited, and any particle shape, such as spherical, needle-like, plate-like, crushed, or scaly, can be used without restrictions.
• inorganic pigments include chromates such as yellow lead, zinc yellow, and barium yellow; ferrocyanides such as iron blue; sulfides such as vermilion, cadmium yellow, zinc sulfide, and cadmium red; sulfates such as barium sulfate, zinc sulfate, and strontium sulfate; oxides such as zinc oxide, antimony white, titanium white, red iron oxide, iron black, and chromium oxide; hydroxides such as aluminum hydroxide; silicates such as calcium silicate and ultramarine; and carbon such as carbon black and graphite.
• chromates such as yellow lead, zinc yellow, and barium yellow
• ferrocyanides such as iron blue
• sulfides such as vermilion, cadmium yellow, zinc sulfide, and cadmium red
• sulfates such as barium sulfate, zinc sulfate, and strontium sulfate
• oxides
• organic pigments examples include nitroso pigments such as Naphthol Green B and Naphthol Green Y; nitro pigments such as Naphthol Yellow S and Xylene Fast Yellow 2G; insoluble azo pigments such as Toluidine Red 4R, Brilliant Fast Scarlet, Hansa Yellow, and Pigment Yellow; sparingly soluble azo pigments such as Lithol Red, Lake Red C, and Lake Red D; soluble azo pigments such as Brilliant Carmine 6B, Toluidine Red F5R, Pigment Scarlet 3B, and Bordeaux 10B; phthalocyanine pigments such as Phthalocyanine Blue, Phthalocyanine Green, and Sky Blue; basic dye pigments such as Rhodamine Lake, Malachite Green Lake, and Methyl Violet Lake; and acid dye pigments such as Peacock Blue Lake, Eosine Lake, Quinoline Yellow Lake, and Aluminum Lake.
• nitroso pigments such as Naphthol Green B and Naphthol Green Y
• inorganic pigments such as titanium white, red iron oxide, iron oxide black, and yellow iron oxide are more preferable because they have better heat resistance and light resistance than organic pigments.
• the content of the colorant in the dental composition of the present invention is not limited as long as it is within the range in which the effects of the present invention can be obtained, but from the viewpoint of aesthetics, it is preferably 0.0005 parts by mass or more, more preferably 0.002 parts by mass or more, even more preferably 0.004 parts by mass or more, and particularly preferably 0.006 parts by mass or more, relative to 100 parts by mass of the total amount of monomers in the dental composition.
• the content of the coloring agent is preferably 2.0 parts by mass or less, more preferably 1.0 part by mass or less, even more preferably 0.5 parts by mass or less, and particularly preferably 0.3% by mass or less, based on 100 parts by mass of the total amount of the monomers in the dental composition. By being equal to or less than the upper limit, the color tone of the natural tooth at the bottom of the cavity can be effectively reflected in the filling part.
• the content of the colorant is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, even more preferably 0.0005% by mass or more, and particularly preferably 0.001% by mass or more, based on the total amount (100% by mass) of the dental composition.
• the content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.07% by mass or less.
• the dental composition of the present invention preferably has a viscosity (shear viscosity) measured at 25°C and a shear rate of 10 s -1 in the range of 1 to 200 Pa ⁇ s, more preferably in the range of 5 to 150 Pa ⁇ s, and even more preferably in the range of 10 to 120 Pa ⁇ s.
• the viscosity was measured by the method described in the Examples below.
• the dental composition of the present invention can be suitably used for dental treatment applications such as self-adhesive dental composite resins and dental cements.
• the total amount of monomers includes 1 to 40 parts by mass of monomer (a) having an acidic group and 60 to 99 parts by mass of monomer (b) not having an acidic group, and that the total amount of monomers includes 0.05 to 10 parts by mass of photopolymerization initiator (c-1), 20 to 500 parts by mass of aggregated filler (d-1), 80 to 400 parts by mass of filler (d-2), and 0.001 to 30 parts by mass of polymerization accelerator (e) relative to 100 parts by mass of the total amount of monomers, and that the total amount of monomers includes 2.5 to 35 parts by mass of monomer (a) having an acidic group and 65 to 97.5 parts by mass of monomer (b) not having an acidic group, and that the total amount of monomers includes 100 parts by mass of the total amount of monomers.
• the composition contains 0.1 to 5 parts by mass of photopolymerization initiator (c-1), 30 to 400 parts by mass of aggregated filler (d-1), 90 to 300 parts by mass of filler (d-2), and 0.01 to 10 parts by mass of polymerization accelerator (e) per 100 parts by mass of the total amount of monomers, and contains 5 to 30 parts by mass of monomer (a) having an acidic group and 70 to 95 parts by mass of monomer (b) not having an acidic group, and further contains 0.15 to 2.5 parts by mass of photopolymerization initiator (c-1), 40 to 300 parts by mass of aggregated filler (d-1), 100 to 200 parts by mass of filler (d-2), and 0.1 to 5 parts by mass of polymerization accelerator (e) per 100 parts by mass of the total amount of monomers.
• the monomer (c-1) is preferably a photopolymerization initiator
• the chemical polymerization initiator (c-2) is preferably a photopolymerization initiator.
• the ...1) is preferably a photopolymerization initiator.
• the chemical polymerization initiator (c-2) is preferably a photopolymerization initiator.
• the chemical polymerization initiator (c-1) is preferably a photopolymerization initiator.
• the chemical polymerization initiator (c-2) is preferably a photopolymerization initiator.
• the chemical polymerization initiator (c) It is more preferable that the composition contains 0.1 to 3 parts by mass of initiator (c-1), 0.1 to 10 parts by mass of chemical polymerization initiator (c-2), 30 to 400 parts by mass of aggregated filler (d-1), 90 to 300 parts by mass of filler (d-2), and 0.01 to 10 parts by mass of polymerization accelerator (e).
• the composition contains 5 to 30 parts by mass of monomer (a) having an acidic group and 70 to 95 parts by mass of monomer (b) not having an acidic group in a total of 100 parts by mass of monomer, and contains 0.15 to 2 parts by mass of photopolymerization initiator (c-1), 0.15 to 5 parts by mass of chemical polymerization initiator (c-2), 40 to 300 parts by mass of aggregated filler (d-1), 100 to 200 parts by mass of filler (d-2), and 0.1 to 5 parts by mass of polymerization accelerator (e) relative to the total amount of 100 parts by mass of monomer.
• the dental composition can be easily produced by a method known to those skilled in the art, comprising a monomer (a) having an acidic group, a monomer (b) not having an acidic group, a polymerization initiator (c), and a filler (d) (aggregated filler (d-1)), and further comprising other components as necessary.
• An example of an embodiment is a method for producing a dental composition by mixing at least three components, namely, a monomer (a) having an acidic group, a monomer (b) not having an acidic group, a polymerization initiator (c), and the aggregated filler (d-1).
• the method for producing the dental composition may be performed by further mixing the filler (d-2) other than the aggregated filler (d-1) and the polymerization accelerator (e) in the above embodiment.
• the dental composition of the present invention may be combined with a dental etching material, a dental primer, a dental bonding material, and the like. From the viewpoint of adhesive strength with tooth structure, it is preferable to combine a dental primer and a dental bonding material, and it is more preferable to combine a dental bonding material.
• the dental primer and the dental bonding material may or may not be polymerized alone, but from the viewpoint of adhesion to the tooth structure, it is preferable to polymerize them by photopolymerization or chemical polymerization.
• the dental primer and the dental bonding material may be used alone or in combination. From the viewpoint of adhesion to the tooth structure, the procedure of applying the dental primer and then the dental bonding material is preferable.
• MDP 10-methacryloyloxydecyl dihydrogen phosphate
• GPDM 1,3-dimethacryloyloxypropyl-2-dihydrogen phosphate
• Agglomerated filler (d-1) Filler 1: Surface-treated SiO 2 -ZrO 2 agglomerated filler Surface-treated SiO 2 -ZrO 2 agglomerated filler (SG-SZ200G151CMP8, average particle size of primary particles: 200 nm, average particle size of secondary particles: 5.2 ⁇ m, refractive index: 1.51, manufactured by Sukyung AT)
• Filler 2 Surface-treated SiO 2 -ZrO 2 agglomerated filler Surface-treated SiO 2 -ZrO 2 agglomerated filler (SG-SZ50G151CMP8, average particle size of primary particles: 50 nm, average particle size of secondary particles: 6.5 ⁇ m, refractive index: 1.51, manufactured by Sukyung AT)
• Filler 3 Surface-treated BaO agglomerated filler 100 parts by mass of barium glass (product name: GM27884, average particle size of primary particles: 180 nm, manufactured by Schott Corporation), 22 parts by
• the slurry solution was sprayed and granulated using a spray dryer (FOC-16, Okawara Kakoki Co., Ltd.)
• the granulated filler was heated in an electric furnace at 700°C for 1 hour to produce BaO agglomerated filler with an average secondary particle size of 7.8 ⁇ m.
• 100 parts by mass of BaO agglomerated filler, 11 parts by mass of 3-methacryloyloxypropyltrimethoxysilane, and 500 mL of 0.5% aqueous acetic acid solution were placed in a three-neck flask and stirred for 2 hours under ultrasonic dispersion at room temperature.
• Filler 4 Surface-treated SiO 2 treated silica Ar130 (hydrophilic fumed silica, ultrafine silica "Aerosil (registered trademark) 130", average particle size: 16 nm, refractive index: 1.46, manufactured by Nippon Aerosil Co., Ltd.) 100 g, 30 g of 3-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3 mass% acetic acid aqueous solution were placed in a three-neck flask and stirred for 2 hours under ultrasonic dispersion at room temperature.
• Filler 4 Surface-treated SiO2- coated YbF3 Surface-treated SiO 2 -coated YbF 3 (SG-YBF100WSCMP10, average particle size of primary particles: 110 nm, average particle size of secondary particles: 1.2 ⁇ m, refractive index: 1.53, manufactured by Sukgyung AT)
• Filler 6 Surface-treated SiO2 filler Silica powder (product name: High Silica, refractive index: 1.55, manufactured by Nichitsu Co., Ltd.) was pulverized with a dry ball mill ( ⁇ 10 mm alumina ball) to obtain pulverized silica powder.
• the average particle size of the obtained pulverized silica powder was measured on a volume basis using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, model "SALD-2300") and was found to be 2.2 ⁇ m.
• 100 g of this pulverized silica powder, 4 g of 3-methacryloyloxypropyltrimethoxysilane, and 200 mL of an aqueous acetic acid solution were placed in a three-necked flask and stirred for 2 hours under ultrasonic dispersion at room temperature. After removing water by freeze-drying, heat treatment was performed at 90 ° C for 3 hours to obtain Filler 6.
• Filler 7 Surface-treated aggregated SiO2 filler Silica microbead P-500 (average particle size of primary particles: 12 nm, average particle size of secondary particles: 2.0 ⁇ m, refractive index: 1.46, manufactured by JGC Catalysts and Chemicals Co., Ltd.) 100 parts by mass, 20 parts by mass of 3-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.5% aqueous acetic acid solution were placed in a three-neck flask and stirred for 2 hours under ultrasonic dispersion at room temperature. After removing water by freeze-drying, heat treatment was performed at 90 ° C for 3 hours to obtain Filler 7.
• Silica microbead P-500 average particle size of primary particles: 12 nm, average particle size of secondary particles: 2.0 ⁇ m, refractive index: 1.46, manufactured by JGC Catalysts and Chemicals Co., Ltd.
• Filler 8 Surface-treated BaO filler 100 parts by mass of barium glass (product name: GM27884, average particle size of primary particles: 0.18 ⁇ m, manufactured by Schott Co.), 11 parts by mass of 3-methacryloyloxypropyltrimethoxysilane, and 500 mL of 0.5% aqueous acetic acid solution were placed in a three-neck flask and stirred for 2 hours under ultrasonic dispersion at room temperature. After removing water by freeze-drying, heat treatment was performed at 90° C. for 3 hours to obtain Filler 8. Table 1 shows an overview of the characteristics of the above-mentioned fillers 1 to 8.
• the constituent elements in Table 1 are metal elements (excluding fluorine) confirmed from the product pamphlet of the manufacturer of the filler raw material or the filler itself.
• the average particle size of the primary particles and secondary particles means a value confirmed from the product pamphlet of the manufacturer of the filler raw material or the filler itself, or a value measured on a volume basis using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, model "SALD-2300”) using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium.
• SALD-2300 laser diffraction particle size distribution measuring device
• the specific surface area means a value measured by the BET multipoint method described later, or a value described in the product pamphlet or inspection report of the manufacturer of the filler itself.
• the specific surface area was measured by the BET multipoint method. Specifically, using a specific surface area measuring device ("BELSORP-mini II" manufactured by Microtrac-Bell Corporation), the specific surface area of the aggregated filler was measured based on the BET method under the conditions of vacuum degassing at 100°C for 2 hours, adsorbed gas: nitrogen, and measurement temperature: 77K. In addition, the measurement results were analyzed by the BET multipoint method using five points on the adsorption side isotherm where the ratio (P/P) of the adsorption equilibrium pressure P (kPa) to the saturated vapor pressure P (kPa) was in the range of 0.05 to 0.3. The results are shown in Table 1.
• TN326 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole (product name: Tinuvin 326, manufactured by BASF Japan Ltd.) (ultraviolet absorber)
• LBL Diethyl 2,5-dihydroxyterephthalate (fluorescent agent)
• BHT 3,5-di-t-butyl-4-hydroxytoluene (polymerization inhibitor)
• Teflon registered trademark
• the smooth surface was polished for 15 seconds at a rotation speed of about 5000 rpm using Compomaster CA (manufactured by Matsukaze Corporation) under water injection conditions.
• the gloss of the obtained polished surface was expressed as a percentage when a mirror was taken as 100% using a gloss meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., VG 7000).
• the measurement angle was 60°.
• the gloss level is preferably 50% or more, more preferably 55% or more, even more preferably 60% or more, and particularly preferably 65% or more.
• Test Example 2 Shear bond strength (enamel, dentin) The test was conducted in accordance with ISO29022:2013. Specifically, the test is as follows: The labial surfaces of bovine teeth were polished with #80 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to obtain samples with the flat surface of the enamel exposed and samples with the flat surface of the dentin exposed. First, the shear bond strength to enamel was measured using a sample with the flat enamel surface exposed, using the following method. Tape was applied to the bottom surface of a separately prepared mold having 15 holes (15-hole mold, manufactured by Ultradent, ⁇ 35 mm ⁇ height 25 mm), and the sample bovine tooth was fixed onto the tape.
• a resin for dental impression trays (trade name "Tray Resin II", manufactured by Matsufu Co., Ltd.) was filled into the mold and left to stand for about 30 minutes to harden the resin for dental impression trays, thereby obtaining a composite of bovine teeth and hardened resin.
• the composite was taken out of the mold as a sample.
• the composite was in a state where the bovine tooth was exposed on the upper surface of the cured resin.
• the upper surface of the sample was polished under running water with #600 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) until the size of the surface to be adhered ( ⁇ 2.38 mm or more) was secured, and the surface to be adhered was ultrasonically washed with water for 5 minutes.
• a separately prepared ⁇ 2.38 mm CR filling mold (Bonding Mold Insert, Ultradent) was attached to a dedicated tool (Bonding Clamp, Ultradent).
• the CR filling mold attached to the dedicated tool was lowered so that the CR filling mold was in close contact with the adhesion surface of the sample, and the sample was fixed.
• the prepared dental composition was thinly filled into the hole of the CR filling mold so that the thickness was within 1 mm.
• the dental composition was filled again into the CR filling mold (up to about 2/3 of the mold, about 2 mm thick), and after leaving it for 10 seconds, the dental composition was hardened by irradiating it with light for 10 seconds using a dental polymerization light irradiator (manufactured by Ultradent, product name "VALO").
• a dental polymerization light irradiator manufactured by Ultradent, product name "VALO"
• the sample was removed from the CR filling mold and used as a test sample for adhesion test.
• Ten test samples for adhesion test were prepared.
• the adhesion test sample was left in a container immersed in distilled water in an incubator set at 37° C. for 24 hours, and immediately after being removed from the distilled water, the shear adhesive strength to enamel was measured.
• the shear adhesive strength to enamel and dentin is preferably greater than 4.0 MPa, more preferably 5.0 MPa or more, even more preferably 6.0 MPa or more, and particularly preferably 8.0 MPa or more.
• Test Example 3 Bending properties (bending strength) The flexural modulus and flexural strength were evaluated by a flexural test in accordance with ISO 4049:2019. Specifically, the following is performed. The prepared paste-like dental composition was filled into a SUS mold (length 2 mm x width 25 mm x thickness 2 mm), and the top and bottom of the paste (2 mm x 25 mm surfaces) were pressed with slide glass.
• a dental polymerization LED light irradiator (PenCure 2000, manufactured by Morita Co., Ltd.) was used to irradiate the paste from above and below to the front and back of the paste through the slide glass (a total of 50 seconds of light irradiation per side) in standard mode for 10 seconds each, dividing the paste into five places on each side, to harden the paste and obtain a hardened product.
• Five hardened products were prepared for each Example and Comparative Example.
• the specimen was immersed in distilled water in a container and left in an incubator set at 37° C.
• the bending strength is preferably 90 MPa or more, more preferably 95 MPa or more, even more preferably 100 MPa or more, particularly preferably 105 MPa or more, and most preferably 110 MPa or more.
• the viscosity measured at 25° C. and a shear rate of 10 s ⁇ 1 is preferably within the range of 1 to 200 Pa ⁇ s, more preferably within the range of 5 to 150 Pa ⁇ s, and even more preferably within the range of 10 to 120 Pa ⁇ s.
• the dental compositions of the examples have abradability of 55% or more, a shear bond strength to enamel of 7 MPa or more, a shear bond strength to dentin of 6 MPa or more, a flexural strength of 100 MPa or more, and a shear viscosity of 33 to 125 s -1 , and are dental compositions that not only have high mechanical strength, excellent abradability, and good paste properties, but also high adhesive strength to tooth tissue.
• Comparative Examples 1 to 3 do not contain the aggregated filler (d-1).
• Comparative Example 1 contains Filler 6, the average primary particle size of which is as large as 2.2 ⁇ m, and therefore has an extremely low polishability of 4%.
• the shear viscosity was high at 211 s -1 , resulting in low fluidity of the monomer and a low adhesive strength to dentin of 3 MPa.
• Comparative Example 3 using Filler 8 has good polishability, but the shear test strength against dentin is low at 4 MPa, and the bending strength is also low at 82 MPa.
• Comparative Example 4 which did not contain the monomer (a) having an acidic group, had a shear test strength against enamel and dentin of only 1 MPa.
• the dental composition of the present invention is suitable for use as a self-adhesive dental composite resin or dental cement in the field of dental treatment.

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