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
  • A61K6/17—Particle size
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/08—Artificial teeth; Making same
  • A61C13/09—Composite teeth, e.g. front and back section; Multilayer teeth
• • 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
  • A61K6/16—Refractive index
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/62—Photochemical radical initiators
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/65—Dyes
• • 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
  • A61K6/70—Preparations for dentistry comprising inorganic additives
  • A61K6/78—Pigments
• • 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
  • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
• • 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
  • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
  • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
• • 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 curable composition and a dental prosthesis. More particularly, it relates to a dental curable composition coating a substrate and a dental prosthesis comprising a substrate and a resin layer.
• metals were often used as dental prostheses (eg, covered crowns, crowns, crowns, false teeth, etc.).
• metals have the drawback of lacking aesthetics, and the elution of metals sometimes causes allergies. Therefore, in order to solve the problems associated with the use of metals, ceramic materials such as aluminum oxide (alumina), zirconium oxide (zirconia), quartz glass, lithium silicate glass, acrylic resins, polymer resins and inorganic fillers are used instead of metals.
• Ceramic materials and the like containing have been used in dental products.
• zirconia is excellent in terms of aesthetics and strength, and its demand is increasing, especially in conjunction with recent price reductions.
• Patent Documents 1 to 5 are known as such prior art.
• Patent Document 1 discloses a dental prosthesis including a resin layer using a polymerizable monomer and a base material, the base material containing zirconia, and the base material being coated with the resin layer. .
• Patent Document 2 discloses a dental prosthesis in which a polymerizable composition (dental composite resin) is built up on a ceramic frame (base material) and polymerized and cured.
• Patent Document 3 discloses coating the surface of a dental material with a coating material containing inorganic fine particles whose surface is decorated with an alkoxysilane having an unsaturated double bond in a (meth)acrylate monomer.
• Patent Document 4 the surface of a dental restoration is coated with a coating material composition containing an ⁇ -diketone compound, an amine compound, and a polymerizable monomer, and polymerized and cured to produce an aesthetic dental restoration. Or a method for protecting tooth substance has been reported.
• Patent Document 5 discloses a dental curable composition excellent in polishing lubricity, containing a polymerizable monomer, an inorganic filler, polyorganosilsesquioxane particles, and a polymerization initiator.
• dental compositions containing polythiol compounds have also been known, for example, as in Patent Documents 7 and 8.
• a PFZ is produced by coating a substrate with a slurry containing a ceramic material that will become a porcelain, and then firing the slurry at several hundred degrees Celsius to bake the porcelain onto the substrate. Therefore, in order to suppress the occurrence of defects during firing, it is necessary to select a porcelain material having a coefficient of thermal expansion close to that of the base material. For example, when using a zirconia sintered body as the base material, it is necessary to select a ceramic material having a thermal expansion coefficient close to that of the zirconia sintered body as the porcelain material.
• Patent Document 1 discloses a method of obtaining a prosthesis by coating with a polymerizable monomer to improve translucency of zirconia as a base material
• Patent Document 2 discloses a method in which alumina is used as a base material.
• a dental prosthesis built up with a polymerizable composition is shown.
• the polymerizable monomer described has a problem that sufficient durability for maintaining luster cannot be maintained under a poor environment in the oral cavity.
• the color tone of the resin layer covering the base material may change due to polymerization and curing, and in addition to transparency, the color tone when the base material is coated may change. There was room for improvement in controlling change.
• the photopolymerizable dental coating material composition described in Patent Document 3 has a problem that gelation occurs during storage and the surface curability decreases over time.
• the material composition has a problem of not being able to maintain sufficient durability to maintain the luster under the poor environment of the oral cavity, and no study has been made on the ceramic material.
• the dental curable composition described in Patent Document 5 is excellent in transparency and the like, there is room for further improvement in terms of glossiness in order to obtain an appearance equivalent to that of natural teeth. It has also been found that there is room for further improvement in the operability in building up the adhesive composition.
• Patent Document 7 relates to a flowable composite, and the dental composition of Patent Document 7 has an excessively high viscosity as a composition, resulting in poor operability when used as a coating for dental prostheses such as zirconia. There was room for improvement. Furthermore, in Patent Document 7, abrasion resistance, lubricity durability, and fluorescence durability were not examined.
• the dental resin composition described in Patent Document 8 is assumed to be used as a solid resin block for dental cutting.
• the dental resin composition described in Patent Document 8 is not intended for use as a coating for dental prostheses such as zirconia in which the dental resin composition is applied onto a base material. Operability that can be formed, suppression of color tone change of the base material, imparting fluorescence to the base material when building up on the base material to make a cured product, lubricating durability of the cured product, and fluorescent durability. The unique challenges in the application of coatings for artificial prostheses have not been explored.
• the present invention provides a dental treatment that can impart fluorescence to a base material, is excellent in operability, can suppress color tone change of the base material, and gives a cured product that is excellent in wear resistance, lubricity durability, and fluorescence durability.
• An object of the present invention is to provide a curable composition for dental use and a dental prosthesis using the same.
• a curable dental composition comprises a polyfunctional thiol (B-1) having two or more mercapto groups in one molecule, and
• the fluorescent agent (C) in combination with other components, the coating layer formed by chemically and mechanically bonding to the base material maintains appropriate hardness, glossiness, and light reflection, and the dental prosthesis It was found that the natural luster and fluorescence can be easily maintained for a long period of time. Furthermore, based on this finding, the inventors further proceeded with the research and completed the present invention.
• the resin layer comprises a polymerizable compound (A), a polyfunctional thiol (B-1), a fluorescent agent (C), and a polymerization initiator (D). It was found that a dental prosthesis comprising a base material coated with a certain thickness containing a polymerized and cured product of a curable composition is useful. was completed.
• the present invention relates to the following inventions.
• a polymerizable compound (A), a polymerization accelerator (B), a fluorescent agent (C), and a polymerization initiator (D) A dental curable composition, wherein the polymerization accelerator (B) contains a polyfunctional thiol (B-1) having two or more mercapto groups in one molecule.
• the polyfunctional thiol (B-1) contains a polyfunctional thiol having 2 to 4 mercapto groups in one molecule.
• the curable dental composition according to any one of [1] to [5]. [7] Any one of [1] to [6], wherein the polymerizable compound (A) comprises a urethane (meth)acrylate oligomer (A-1) and/or a polymerizable monomer (A-2) The dental curable composition according to . [8] The dental curable composition according to [7], wherein the polymerizable monomer (A-2) is a (meth)acrylic polymerizable monomer. [9] The dental curable composition according to any one of [1] to [8], wherein the polymerization initiator (D) contains a photopolymerization initiator (D-1).
• a dental prosthesis comprising a resin layer obtained by polymerizing and curing the dental curable composition according to any one of [1] to [17], and a base material.
• the substrate comprises at least one selected from the group consisting of zirconia, alumina, quartz glass, lithium silicate glass, acrylic resin, and a composite material containing a polymer resin and an inorganic filler.
• the zirconia contains zirconia and a stabilizer capable of suppressing phase transition of zirconia.
• the resin layer has a thickness of 1 ⁇ m to 500 ⁇ m.
• the present invention it is possible to impart fluorescence to a substrate, to be excellent in operability, to suppress color tone change of the substrate, and to give a cured product with wear resistance, lubricity durability, and fluorescence durability.
• An excellent dental curable composition and a dental prosthesis using the same can be provided.
• the dental curable composition has excellent curability and can be polymerized and cured in a short time.
• the resin layer covering the surface has appropriate hardness, chemically and mechanically adheres to the base material, improves wear resistance, and is a mating natural tooth or prosthesis. It is possible to provide a dental curable composition and a dental prosthesis that can protect the substrate itself from wear and maintain long-term fluorescence and gloss.
• normal temperature strictly means 25°C.
• the polymerizable compound (A) included in the present invention preferably contains a urethane (meth)acrylate oligomer (A-1).
• the urethane (meth)acrylate oligomer (A-1) is used to impart hardness, wear resistance and toughness to the cured product of the curable dental composition of the present invention. Further, the urethane (meth)acrylate oligomer (A-1) contributes to curability and toughness of the cured product when combined with the polymerizable monomer (A-2) described later.
• “(meth)acryl” means methacryl and acryl
• “(meth)acryloyl” means methacryloyl and acryloyl.
• the urethane (meth)acrylate oligomer (A-1) used in the dental curable composition of the present invention is an oligomer having a urethane bond (—NHC(O)O—), and in addition to the urethane bond, In addition, it may have at least one structure selected from the group consisting of polyesters, polyethers, polycarbonates, polyurethanes, and polyconjugated dienes.
• the viscosity of the urethane (meth)acrylate oligomer (A-1) at 25° C. is preferably 4000 to 250000 mPa ⁇ s, more preferably 6000 to 200000 mPa ⁇ s. 8000 to 150000 mPa ⁇ s is more preferable.
• the viscosity can be measured, for example, at 25° C. and 20 rpm with a Brookfield viscometer.
• the pencil hardness of the cured film (cured product) of the urethane (meth)acrylate oligomer (A-1) is preferably F or higher, more preferably H or higher, and even more preferably 2H or higher.
• the pencil hardness of the cured film can be measured according to JIS K 5600-5-4:1999, for example.
• the above urethane (meth)acrylate oligomer (A-1) can provide preferable curability, viscosity and hardness of the cured product when combined with the polymerizable monomer (A-2) described later.
• a preferred embodiment is a curable dental composition in which the urethane (meth)acrylate oligomer (A-1) is a urethane acrylate oligomer, in view of the superior effects of the present invention.
• the urethane (meth)acrylate oligomer (A-1) includes, for example, urethane acrylate oligomers "EBECRYL8807”, “EBECRYL8465”, “EBECRYL8800”, “EBECRYL4101”, “EBECRYL4201", which are commercially available from Daicel Allnex Co., Ltd.
• Viscosity 10,000 to 40,000 mPa s, pencil hardness of cured film: 6H
• pentaerythritol triacrylate toluene diisocyanate urethane prepolymer "UA-306T” viscosity at 25 ° C.: 10,000 to 40,000 mPa s, pencil hardness of cured film: 5H
• U-306T viscosity at 25 ° C.: 10,000 to 40,000 mPa s, pencil hardness of cured film: 5H
• One of these may be used alone, two or more of them may be used in combination, and a polymer of a mixture thereof may be used.
• the content of the urethane (meth)acrylate oligomer (A-1) is preferably 25 to 55% by mass, more preferably 30 to 50%, based on the total amount of the dental curable composition. % by mass is more preferred, and 35 to 45% by mass is even more preferred. Further, the content of the urethane (meth)acrylate oligomer (A-1) is preferably 30 to 80% by mass, more preferably 35 to 75% by mass, and 40 to 70% by mass is more preferred.
• the polymerizable compound (A) included in the present invention preferably contains a polymerizable monomer (A-2).
• the polymerizable monomer (A-2) is used to enhance curability and adhesion to substrates.
• the polymerizable monomer (A-2) also contributes to the curability of the cured product when combined with the urethane (meth)acrylate oligomer (A-1).
• the polymerizable monomer (A-2) known polymerizable monomers used in dental compositions can be used without any limitation.
• the polymerizable monomer (A-2) may be a monomer having no acidic group.
• Specific examples of the polymerizable monomer (A-2) include ⁇ -cyanoacrylic acid, (meth)acrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid and itaconic acid.
• (meth)acrylic acid esters or (meth)acrylamide (meth)acrylic polymerizable monomers are preferably used.
• the (meth)acrylic polymerizable monomer which is the (meth)acrylic acid ester polymerizable monomer or the (meth)acrylamide polymerizable monomer, include monofunctional (meth)acrylates, monofunctional (meth) ) Monofunctional monomers such as acrylamide, and polyfunctional monomers such as bifunctional (meth)acrylates and trifunctional or higher (meth)acrylates.
• the "polyfunctional monomer” means a mercapto group of a polyfunctional thiol (B-1) such as a vinyl group, (meth)acryloyl group, (meth)acrylamide group, etc. It means a monomer having two or more polymerizable groups other than Examples of suitable polymerizable monomers (A-2) are shown below.
• - Bifunctional (meth) acrylate monomer (a-2) Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth) ) acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propoxylated (2) neopentyl glycol di(meth)acrylate , glycerin di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-hydroxy-3
• the polymerizable monomer (A-2) is preferably a trifunctional or higher (meth)acrylate monomer (a-3) from the viewpoint of curability. More preferred are pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and ethoxylated (3) trimethylolpropane triacrylate.
• the polymerizable monomer (A-2) may be blended singly or in combination of two or more.
• polyfunctional monomers preferably polyfunctional (meth)acrylate monomers
• the content of the polymerizable monomer (A-2) is preferably 20 to 55% by mass, more preferably 25 to 50% by mass, based on the total amount of the dental curable composition. % is more preferred, and 30 to 45% by mass is even more preferred. Further, the content of the polymerizable monomer (A-2) is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, based on 100 parts by mass of the total amount of the polymerizable compound (A), and 30 to 70% by mass. % by mass is more preferred.
• the polymerizable compound (A) contains a polymerizable monomer (A-2), and the polymerizable monomer (A-2) has at least one acidic group per molecule. and an adhesive monomer (a-4) having an acidic group (hereinafter also referred to as "adhesive monomer (a-4) having an acidic group").
• adhesive monomer (a-4) having an acidic group hereinafter also referred to as "adhesive monomer (a-4) having an acidic group”
• a dental adhesive composition (G) containing an adhesive monomer (a-4) having an acidic group may be used with the dental hardenable composition of the present invention.
• a preferred embodiment is a dental kit comprising the dental curable composition of the present invention and a dental adhesive composition (G) containing an acidic group-containing adhesive monomer (a-4). is mentioned.
• the dental curable composition of the present invention used in the dental kit may or may not contain the adhesive monomer (a-4) having an acidic group.
• the dental adhesive composition (G) contains a volatile organic solvent (H) in addition to the adhesive monomer (a-4) having an acidic group
• "primer composition (G)” called.
• a commercially available product for example, the product name "Clearfill (registered trademark) Ceramic Primer Plus” (manufactured by Kuraray Noritake Dental Co., Ltd.), etc.
• the adhesive composition (G) containing the adhesive monomer (a-4) having an acidic group strengthens the interface between the substrate and the cured product of the composition, which is the resin layer built up on the substrate. Can be glued.
• the adhesive monomer (a-4) having an acidic group is a polymerizable monomer having an acidic group such as a phosphoric acid group, a phosphonic acid group, a pyrophosphate group, a thiophosphoric acid group, a carboxylic acid group or a sulfonic acid group. Specific examples include the following.
• Phosphate group-containing polymerizable monomers include, for example, 2-(meth)acryloyloxyethyl dihydrogenphosphate, 10-(meth)acryloyloxydecyldihydrogenphosphate, 20-(meth)acryloyloxyeicosyldi hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogenphosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethylphosphorus Acids, (meth)acryloyloxyethylphenylphosphonates, etc., and acid chlorides thereof.
• Phosphonic acid group-containing polymerizable monomers include, for example, 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl -3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexylphosphonoacetate, 10-(meth)acryloyloxydecylphosphonoacetate, and acid chlorides thereof.
• Pyrophosphate group-containing polymerizable monomers include, for example, di[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)pyrophosphate ) acryloyloxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and acid chlorides thereof.
• polymerizable monomers having a thiophosphoric acid group examples include 2-(meth)acryloyloxyethyl dihydrogendithiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, and acid chlorides thereof. is mentioned.
• carboxylic acid group-containing polymerizable monomers examples include (meth)acrylic acid, mono(2-(meth)acryloyloxyethyl) succinate, mono(2-(meth)acryloyloxyethyl) isophthalate, N- (Meth) acryloyl-5-aminosalicylic acid, 4-vinylbenzoic acid, 4-(meth) acryloyloxyethoxycarbonyl phthalic acid, 4-(meth) acryloyloxyethoxycarbonyl phthalic anhydride, 5-(meth) acryloylaminopentyl Carboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid and the like, and acid chlorides thereof.
• the sulfonic acid group-containing polymerizable monomer examples include p-styrenesulfonic acid and the like.
• a phosphoric acid group-containing polymerizable monomer or a phosphonic acid group-containing polymerizable monomer is preferable from the viewpoint of excellent interfacial adhesiveness.
• Phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethylphenyl phosphonate are preferred.
• These adhesive monomers (a-4) having an acidic group may be used singly or in combination of two or more.
• the content of the adhesive monomer (a-4) having an acidic group in the adhesive composition (G) is not particularly limited, but the total amount of the adhesive composition (G) is 0.1 to 10% by mass. is preferred, 1 to 5 mass % is more preferred, and 1 to 3 mass % is even more preferred.
• the content of the adhesive monomer (a-4) having an acidic group is the polymerizable compound (A) Of the total amount of 100% by mass, preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and even more preferably 5 to 25% by mass.
• the polymerization accelerator (B) contains a polyfunctional thiol (B-1) having two or more mercapto groups in one molecule.
• the polymerization accelerator (B) contains only polyfunctional thiol (B-1) having two or more mercapto groups in one molecule as a compound having a mercapto group. things are mentioned.
• the embodiment may contain a polymerization accelerator (B-2) other than the polyfunctional thiol (B-1).
• Another embodiment includes a dental curable composition in which the polymerization accelerator (B) is a polyfunctional thiol (B-1) having two or more mercapto groups in one molecule.
• Certain other embodiments also include dental hardenable compositions that are free of monofunctional thiol compounds.
• Polyfunctional thiol (B-1) the polyfunctional thiol (B-1) having two or more mercapto groups in one molecule included in the present invention (hereinafter also referred to as "polyfunctional thiol (B-1)") will be described.
• Polyfunctional thiol (B-1) used in the present invention is a compound having two or more mercapto groups in one molecule, in the presence of the polymerizable compound (A), with a polymerization initiator (D) described later. By combining them, it is possible to promote the curability of the polymerizable compound (A), improve the crosslink density, and obtain a strong cured product having higher impact resistance.
• the use of the polyfunctional thiol (B-1) instead of the monofunctional thiol accelerates the photocrosslinking reaction and improves the curability.
• the cured product has the desired pencil hardness.
• the cured product of the curable dental composition has excellent abrasion resistance.
• the content of the polymerization initiator (D) can be reduced, and shrinkage during curing can be suppressed.
• multiple mercapto groups possessed by the polyfunctional thiol (B-1) can improve the adhesion performance between the resin layer and the base material.
• the sulfur atoms present therein can increase the refractive index. Therefore, by combining the fluorescent agent (C) and the polyfunctional thiol (B-1), while imparting fluorescence to the substrate, the change in color tone when the substrate is coated with the dental curable composition can be improved. can be suppressed. While imparting fluorescence to the substrate, the effect of being able to suppress the color change of the substrate is due to the multiple mercapto groups possessed by the polyfunctional thiol (B-1).
• the curable dental composition of the present invention contains a polyfunctional thiol (B-1), so that it contains a fluorescent agent when it is built up on a base material in the application of coating a dental prosthesis such as zirconia. Fluorescence can be imparted to a base material that is not
• the polyfunctional thiol (B-1) is not particularly limited as long as it is a compound having two or more mercapto groups in one molecule.
• "Polyfunctional” in “polyfunctional thiol (B-1)” means that the number of mercapto groups in one molecule is two or more. Specific examples include a compound having two mercapto groups in one molecule, a compound having three mercapto groups in one molecule, a compound having four mercapto groups in one molecule, and a compound having six mercapto groups in one molecule. compounds having one mercapto group.
• a polyfunctional thiol having 2 to 4 mercapto groups in one molecule is preferable because it has an excellent effect of improving curability and can shorten the curing time, and three mercapto groups in one molecule.
• a polyfunctional thiol having a group and a polyfunctional thiol having 4 mercapto groups in one molecule are more preferable.
• Examples of compounds having two mercapto groups in one molecule include butanediol bis(2-mercaptoacetate), hexanediol bis(2-mercaptoacetate), ethanediol bis(2-mercaptoacetate), butanediol bis(2-mercaptoacetate), (3-mercaptopropionate), 2,2′-(ethylenedithio)diethanethiol, ethylene glycol bis(3-mercapto-2-methylpropionate), ethylene glycol bis(3-mercaptopropionate), Propylene glycol bis(3-mercaptopropionate), diethylene glycol bis(3-mercaptopropionate), octanediol bis(3-mercaptopropionate), propylene glycol bis(3-mercapto-2-methylpropionate) , diethylene glycol bis (3-mercapto-2-methylpropionate), butanediol bis (3-mercapto-2-methylpropionate), o
• the term "primary mercapto group” means a mercapto group bonded to a primary carbon atom
• secondary mercapto group refers to a mercapto group bonded to a secondary carbon atom
• tertiary mercapto group means a mercapto group attached to a tertiary carbon atom.
• a mercapto group is bound to a secondary carbon atom or a tertiary carbon atom” means that the polyfunctional thiol (B-1) has a secondary mercapto group or a tertiary mercapto group means to have
• Examples of compounds having three mercapto groups in one molecule include trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3- mercapto-2-methylpropionate), 3-(3-mercapto-propoxy)-2,2-bis-(3-mercapto-propoxymethyl)-propan-1-ol, etc.
• 3 1 per molecule compounds having a mercapto group trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (4-mercaptovalerate), 3-mercaptovalerate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, etc. and compounds having three tertiary mercapto groups in one molecule such as trimethylolpropane tris(2-mercaptoisobutyrate).
• examples of compounds having four mercapto groups in one molecule include pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), etc. compounds having a mercapto group; Mercapto-2-propionate), pentaerythritol tetrakis (4-mercaptovalerate), compounds having four secondary mercapto groups in one molecule such as pentaerythritol tetrakis (3-mercaptovalerate); pentaerythritol tetrakis ( 2-mercaptoisobutyrate) having four tertiary mercapto groups in one molecule.
• examples of compounds having 6 mercapto groups in one molecule include 6 primary mercapto groups in one molecule such as dipentaerythritol hexakis (3-mercapto-2-methylpropionate) Dipentaerythritol hexakis (3-mercaptobutyrate), dipentaerythritol hexakis (2-mercaptopropionate), dipentaerythritol hexakis (4-mercaptovalerate), dipentaerythritol hexakis ( Compounds having six secondary mercapto groups in one molecule such as 3-mercaptovalerate); six tertiary mercapto groups in one molecule such as dipentaerythritol hexakis (2-mercaptoisobutyrate) and compounds having
• polyfunctional thiols (B-1) compounds having a secondary mercapto group or having a tertiary mercapto group are preferred, suppressing the unpleasant odor of the curable composition and improving storage stability.
• a compound having no primary mercapto group and having a total number of secondary mercapto groups and tertiary mercapto groups of 2 or more is more preferable.
• polyfunctional thiol (B-1) for example, a compound having two secondary mercapto groups in one molecule, a compound having two tertiary mercapto groups in one molecule, three in one molecule compounds having two secondary mercapto groups, compounds having three tertiary mercapto groups in one molecule, compounds having four secondary mercapto groups in one molecule, compounds having four secondary mercapto groups in one molecule
• a compound having a tertiary mercapto group, a compound having six secondary mercapto groups in one molecule, and a compound having six tertiary mercapto groups in one molecule are preferred, and two A compound having a secondary mercapto group, a compound having two tertiary mercapto groups in one molecule, a compound having three secondary mercapto groups in one molecule, three tertiary mercapto groups in one molecule mercapto groups, compounds having four secondary mercapto groups in one molecule, compounds having four
• polyfunctional thiol (B-1) examples include 3-(3-mercapto-propoxy)-2,2-bis-(3-mercapto-propoxymethyl)-propan-1-ol, pentaerythritol tetrakis (3-mercaptobutyric rate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3- mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are particularly preferred.
• the polyfunctional thiol (B-1) may be used alone or in combination of two or more. Further, the molecular weight of the polyfunctional thiol (B-1) is not particularly limited, but from the viewpoint of improving the curability of the curable composition, it is preferably 200 to 1000.
• the polyfunctional thiol (B-1) can also be easily obtained as a commercial product.
• a commercially available polyfunctional thiol having two or more mercapto groups in one molecule 1,4-bis (3-mercaptobutyryloxy) butane (trade name manufactured by Showa Denko Co., Ltd.
• Kerens MT registered trademark
• PE1 pentaerythritol tetrakis (3-mercaptobutyrate)
• 1,3,5-tris (3 -mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione
• TPMB trimethylolpropane tris(3-mercaptobutyrate)
• the refractive index of the polyfunctional thiol (B-1) is preferably 1.40 or higher, more preferably 1.45 or higher, and even more preferably 1.50 or higher, from the viewpoint of the gloss of the cured product.
• the refractive index of the polyfunctional thiol (B-1) can be measured with an Abbe refractometer.
• the refractive index can be measured by partially modifying JIS K 0062:1992. Specifically, it can be measured by an immersion method at 23° C. using an Abbe refractometer and using the D-line of sodium as a light source.
• liquid two or more liquids having a refractive index close to the assumed refractive index of the sample filler (polyfunctional thiol (B-1)) are combined to prepare a plurality of liquids having different refractive indices.
• a sample is suspended in each liquid in an atmosphere of 23° C., and the liquid that looks most transparent is selected by naked eye observation.
• the refractive index of the liquid is used as the refractive index of the sample, and the refractive index of the liquid is measured with an Abbe refractometer.
• Liquids that can be used are, for example, sulfur-dissolved diiodomethane, 1-bromonaphthalene, methyl salicylate, dimethylformamide, 1-pentanol, and the like.
• the content of the polyfunctional thiol (B-1) is preferably 5 to 40% by mass, preferably 10 to 40% by mass, based on the total amount of the curable dental composition. 35% by mass is more preferable, and 15 to 30% by mass is even more preferable. If the content of the polyfunctional thiol (B-1) in the curable composition is within the above range, less odor before and after curing of the curable composition, curing with improved curability and adhesion to the substrate you get something.
• the number of unsaturated groups in the polymerizable compound (A) means the total number (number of moles) of unsaturated groups in all compounds belonging to the polymerizable compound (A).
• the number of mercapto groups in the functional thiol (B-1) means the total number (number of moles) of mercapto groups in all compounds belonging to the polyfunctional thiol (B-1).
• fluorescent agent (C) included in the present invention, one or more of those that can be selected from commonly available fluorescent agents and can emit fluorescence with light of any wavelength. can be used.
• fluorescent agents that are used for dental purposes are preferably used.
• Examples of fluorescent agents (C) include inorganic fluorescent agents (C-1) and organic fluorescent agents (C-2).
• the fluorescent agent (C) can be used singly or in an appropriate combination of two or more.
• the fluorescent agent (C) preferably contains an organic fluorescent agent (C-2) from the viewpoint of easily imparting fluorescence uniformly.
• Examples of the inorganic fluorescent agent (C-1) include those containing a metal element.
• Examples of the metal elements include Ga, Bi, Ce, Nd, Sm, Eu, Gd, Tb, Dy, and Tm.
• the fluorescent agent may contain one of these metal elements alone, or may contain two or more of them. Among these metal elements, Ga, Bi, Eu, Gd and Tm are preferred, and Bi and Eu are more preferred.
• Examples of the fluorescent agent include oxides, hydroxides, acetates, and nitrates of the above metal elements.
• the fluorescent agents are Y 2 SiO 5 :Ce, Y 2 SiO 5 :Tb, (Y, Gd, Eu)BO 3 , Y 2 O 3 :Eu, YAG:Ce, ZnGa 2 O 4 :Zn, BaMgAl 10 It may be O 17 :Eu or the like.
• the content of the inorganic fluorescent agent (C-1) is preferably 0.01 to 30% by mass in the total amount of the dental curable composition, from the viewpoint of expressing fluorescence equivalent to that of human natural teeth, and 0.1 ⁇ 20% by mass is more preferable, and 1 to 10% by mass is even more preferable. If the amount is less than 0.01% by mass, the expression of fluorescence may be insufficient compared to natural human teeth, and the aesthetic appearance may be impaired. It may deteriorate and become patchy fluorescence, which may be unnatural.
• a ratio of up to 100:200 is more preferable, and a ratio of 100:0.1 to 100:100 is more preferable because the effect of suppressing color tone change of the base material, the durability of lubrication, and the durability of fluorescence are excellent.
• organic fluorescent agent (C-2) examples include phthalic acid derivatives (diethyl 2,5-dihydroxyterephthalate, o-phthalaldehyde, etc.), thiophene derivatives (2,5-bis(5'-t-butylbenzoxoxa zolyl-2′)thiophene, 2,5-bis(6,6′-bis(tert-butyl)-benzoxazol-2-yl)thiophene), naphthalene derivatives (1,4-bis(2-benzoxazoly naphthalene), coumarin derivatives (3-phenyl-7-(4-methyl-5-phenyl-1,2,3-triazol-2-yl)coumarin, 3-phenyl-7-(2H-naphtho[1, 2-d]-triazol-2-yl)coumarin), naphthalimide derivative (N-methyl-5-methoxynaphthalimide), stilbene derivative (4,4'-bis(diphenyltriazin
• R 1 and R 2 are each independently an alkyl group, R 3 is a hydrogen atom, an amino group, or a hydroxyl group, and R 4 is an amino group or a hydroxyl group.
• the compound represented by can be mentioned.
• the alkyl group for R 1 and R 2 preferably has 1 to 3 carbon atoms such as methyl group, ethyl group, n-propyl group and isopropyl group, more preferably methyl group and ethyl group.
• Examples of the compound represented by formula (1) include dimethyl 2,5-dihydroxyterephthalate, diethyl 2,5-dihydroxyterephthalate, dimethyl 2-aminoterephthalate, and diethyl 2-aminoterephthalate. - diethyl dihydroxyterephthalate is particularly preferred.
• the content of the organic fluorescent agent (C-2) is preferably 0.001 to 10% by mass, more preferably 0.01 to 8% by mass, from the viewpoint of expressing fluorescence equivalent to that of human natural teeth. 0.05 to 5 mass % is more preferred. If the amount is less than 0.001% by mass, the expression of fluorescence may be insufficient compared to natural human teeth, and the aesthetic appearance may be impaired. Compared to teeth, the expression of fluorescence is too strong, and there is a risk of it becoming unnatural.
• the polymerization initiator (D) can be selected from commonly available polymerization initiators, and polymerization initiators used for dental purposes are particularly preferably used.
• the polymerization initiator (D) includes a photopolymerization initiator (D-1) or a chemical polymerization initiator (D-2).
• a polymerization initiator (D) can be used individually by 1 type or in combination of 2 or more types as appropriate.
• the polymerization initiator (D) preferably contains a photopolymerization initiator (D-1) from the viewpoint of surface curability.
• Examples of the photopolymerization initiator (D-1) include ⁇ -diketones, ketals, thioxanthones, acylphosphine oxides, and ⁇ -aminoacetophenones.
• ⁇ -diketones include dl-camphorquinone, benzyl, and 2,3-pentanedione.
• Ketals include benzyl dimethyl ketal and benzyl diethyl ketal.
• Thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.
• Acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(benzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl) ) phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3 ,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl di(2,6-dimethylphenyl)phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, water-soluble acyl compounds disclosed in JP-B-
• ⁇ -Aminoacetophenones include 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-1-butanone, 2 -benzyl-dimethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-dimethylamino-1-( 4-morpholinophenyl)-1-pentanone, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-1-pentanone.
• the photopolymerization initiator (D-1) one type may be used alone, or two or more types may be used in combination.
• the content of the photopolymerization initiator (D-1) is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 12 parts by mass, with respect to 100 parts by mass of the total amount of the polymerizable compound (A). 0.1 to 10 parts by mass is more preferable.
• the photopolymerization initiator (D-1) may be used alone, and in order to promote photocurability, tertiary amines, aldehydes, polyfunctional thiols such as monofunctional thiols (B- It may be used in combination with a polymerization accelerator (B-2) other than 1) (hereinafter also referred to as another polymerization accelerator (B-2)).
• B-2 polymerization accelerator
• Tertiary amines include 2-(dimethylamino)ethyl (meth)acrylate, N,N-bis[(meth)acryloyloxyethyl]-N-methylamine, N-methyldiethanolamine di(meth)acrylate, N - ethyldiethanolamine di(meth)acrylate, triethanolamine mono(meth)acrylate, triethanolamine di(meth)acrylate, triethanolamine tri(meth)acrylate, triethanolamine, trimethylamine, triethylamine, tributylamine, N-methyl Aliphatic tertiary amines such as diethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine; 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino)butyl benzoate, Aromatic tertiary amines such as 4-(N,N-dimethylamino)butoxy
• Aldehydes include dimethylaminobenzaldehyde and terephthalaldehyde.
• Examples of monofunctional thiols include compounds having one mercapto group in one molecule, such as 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.
• the other polymerization accelerator (B-2) may be used alone, or two or more of them may be used in combination if necessary.
• the content of the other polymerization accelerator (B-2) is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 12 parts by mass, with respect to 100 parts by mass of the total amount of the polymerizable compound (A). , and more preferably 0.1 to 10 parts by mass.
• a redox polymerization initiator consisting of an oxidizing agent and a reducing agent is preferable.
• a redox polymerization initiator it is necessary to divide the packaging form of the polymerizable compound (A) into two or more so that the oxidizing agent and the reducing agent are separated from each other.
• oxidizing agents for redox polymerization initiators include organic peroxides such as diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides.
• diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide and the like.
• peroxyesters include t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxy-2-ethylhexa Noate, t-butylperoxyisopropyl carbonate.
• dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide and lauroyl peroxide.
• peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane.
• ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl acetoacetate peroxide.
• hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide and p-diisopropylbenzene peroxide.
• aromatic tertiary amines aromatic tertiary amines, aliphatic tertiary amines, sulfinic acid and salts thereof are preferred.
• Aromatic tertiary amines include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N- Dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl- 4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-di(2 -hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl
• Aliphatic tertiary amines include trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2-(dimethylamino)ethyl methacrylate, N- Methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate.
• Sulfinic acid and salts thereof include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, p-toluenesulfinic acid, sodium p-toluenesulfinate, and p-toluenesulfinic acid.
• potassium calcium p-toluenesulfinate, lithium p-toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate , 2,4,6-trimethylbenzenesulfinate calcium, 2,4,6-trimethylbenzenesulfinate lithium, 2,4,6-triethylbenzenesulfinic acid, 2,4,6-triethylbenzenesulfinate sodium, 2, 4,6-triethylbenzenesulfinate potassium, 2,4,6-triethylbenzenesulfinate calcium, 2,4,6-triethylbenzenesulfinate lithium, 2,4,6-triisopropylbenzenesulfinate, 2,4, sodium 6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6
• the oxidizing agent and reducing agent may be used singly, or two or more of them may be used in combination, if necessary.
• the content of the oxidizing agent and the reducing agent is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 12 parts by mass, with respect to 100 parts by mass of the total amount of the polymerizable compound (A). .1 to 10 parts by mass is more preferable.
• the dental curable composition of the present invention may contain fillers in order to increase mechanical strength and wear resistance, and to adjust applicability, fluidity, etc. during application.
• An inorganic filler, an organic filler, or an inorganic/organic composite filler can be used as the filler (E).
• inorganic fillers examples include silica - based minerals such as silica , kaolin , clay , mica , and mica ; Ceramics or glasses containing O 3 , SrO 2 , CaO, P 2 O 5 and the like can be mentioned.
• Such glass include lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, zinc glass, fluoroaluminosilicate glass, boron Silicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, and bioglass.
• inorganic fillers crystalline quartz, hydroxyapatite, alumina, titania, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, fluoride Also included are calcium, ytterbium fluoride, and yttrium fluoride. Among these, silica, alumina and titania are preferred, and silica is more preferred.
• the average primary particle size of the inorganic filler is preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less, from the viewpoint of improving the strength of the cured product. From the viewpoint of viscosity of the composition, the average primary particle size is preferably 15 nm or more, more preferably 20 nm or more, and even more preferably 25 nm or more. The range may be any combination of these.
• the average primary particle size is, for example, preferably 15 to 100 nm, more preferably 20 to 90 nm, even more preferably 25 to 80 nm.
• the average particle size of the inorganic filler means the average particle size before the surface treatment.
• the inorganic filler is preferably hydrophobic from the viewpoint of improving the affinity with the polymerizable compound (A) and/or the polyfunctional thiol (B-1) and improving the antifouling property.
• the degree of methanol hydrophobicity of the inorganic filler is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more.
• One embodiment includes a dental curable composition in which the filler (E) comprises hydrophobic silica (E-1) as an inorganic filler.
• the inorganic filler is preferably surface-treated with a surface-treating agent from the viewpoint of enhancing interaction with polysiloxane (F) and improving affinity. This suppresses aggregation of the inorganic filler, reduces the viscosity of the composition, and improves the strength and wear resistance of the cured product.
• a silane coupling agent etc. are mentioned as a surface treating agent.
• Silane coupling agents include, but are not limited to, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropy
• the shape of the particles is not particularly limited, and it can be used as a powder of irregular or spherical particles.
• the average primary particle size can be determined by a laser diffraction scattering method or electron microscope observation of particles.
• the laser diffraction scattering method is convenient for measuring the particle size of 0.1 ⁇ m or more
• the electron microscope observation is convenient for measuring the particle size of ultrafine particles of less than 0.1 ⁇ m.
• 0.1 ⁇ m is a value measured by a laser diffraction scattering method.
• a 0.2% sodium hexametaphosphate aqueous solution is used as a dispersion medium, and the particle size distribution can be measured on a volume basis with a laser diffraction particle size distribution analyzer (SALD-2300, manufactured by Shimadzu Corporation).
• a scanning electron microscope (SU3800, S-4000, manufactured by Hitachi High-Technologies Corporation, etc.) can be used for electron microscope observation.
• For electron microscopic observation take an electron micrograph of the particles, and measure the particle diameter of the particles (200 or more) observed in the unit field of view of the photograph, using image analysis type particle size distribution measurement software (Mac-View (manufactured by Mountech Co., Ltd.) )).
• Mac-View manufactured by Mountech Co., Ltd.
• the particle diameter is obtained as an arithmetic mean value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.
• organic fillers examples include polymethyl methacrylate, polyethyl methacrylate, copolymers of polymethyl methacrylate and polyethyl methacrylate, polyfunctional methacrylate polymers, ethylene-vinyl acetate copolymers, acrylonitrile-butadiene-styrene copolymers, and polyamides. , polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, styrene-butadiene rubber.
• inorganic/organic composite fillers examples include those in which an inorganic filler is dispersed in an organic filler, and those in which the surface of an inorganic filler is coated with various polymerizable monomers (A-2).
• the filler (E) may be used singly or in combination of two or more if necessary.
• the content of the filler (E) is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less in the total amount of the dental curable composition. preferable.
• it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more.
• the range may be any combination of these.
• the content of the filler (E) is, for example, preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, even more preferably 1.0 to 5.0% by mass.
• the present invention may also contain polysiloxane (F).
• Polysiloxane (F) is not particularly limited as long as it is a polymer in which silicon atoms are bonded to each other via oxygen atoms and at least some of the silicon atoms are bonded to organic groups.
• Polysiloxane (F) improves adhesion to substrates (preferably ceramic substrates).
• Polysiloxane (F) may be used individually by 1 type, and may use 2 or more types together.
• a preferred embodiment includes a dental curable composition in which polysiloxane (F) contains polysilsesquioxane (F-1). A preferred embodiment is described below using polysilsesquioxane (F-1).
• the polysilsesquioxane (F-1) included in the present invention improves adhesion to substrates (preferably ceramic substrates). Further, the polysilsesquioxane (F-1), when combined with the filler (E), acts with the filler (E) to improve the affinity with the polymerizable compound (A), resulting in the strength of the cured product. can be improved.
• the polysilsesquioxane (F-1) is not particularly limited as long as it is a linear, branched or network compound having a Si—O bond (siloxane bond).
• Examples of the polysilsesquioxane (F-1) include those composed of units represented by the following general formula (2).
• n 1 in the case of polysilsesquioxane (F-1).
• RnSiO (4-n)/2 (2) (Wherein, R represents an organic group. n represents a number greater than 0 and less than 4.)
• R in the general formula (2) examples include an alkyl group, a cycloalkyl group, a haloalkyl group, an alkenyl group, an aryl group, an arylalkyl group and the like.
• alkyl group examples include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group and butyl group.
• the cycloalkyl group includes cycloalkyl groups having 3 to 10 carbon atoms such as cyclopentyl group and cyclohexyl group.
• Haloalkyl groups include halogenated alkyl groups having 1 to 10 carbon atoms such as 3-chloropropyl group and 3,3,3-trifluoropropyl group.
• the alkenyl group includes alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group and butenyl group.
• the aryl group includes aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group and naphthyl group. Examples of the arylalkyl group include C1-4 alkyl groups having a C6-12 aryl group such as a benzyl group and a phenethyl group.
• R is preferably a methyl group, a phenyl group, an alkyl group, an alkenyl group (such as a vinyl group), or a fluoro C1-6 alkyl group.
• polysilsesquioxanes (F-1) include polydialkylsiloxanes such as polydimethylsiloxane; polyalkylalkenylsiloxanes such as polymethylvinylsiloxane; polyalkylarylsiloxanes such as polymethylphenylsiloxane; polydiarylsiloxane; the copolymer composed of the polyorganosiloxane unit [dimethylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer, dimethylsiloxane-methyl (3,3,3-tri fluoropropyl)siloxane copolymer, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer, etc.] and the like. Polysilsesquioxane (F-1) may be used alone or in combination of two or more
• the polysilsesquioxane (F-1) a composition obtained by heat-treating an organosilicon compound such as a silane coupling agent can be used.
• an organosilicon compound such as a silane coupling agent
• a composition obtained by dissolving a silane coupling agent in a solvent and heating at 70°C for 3 hours to obtain a sol solution, and then distilling off the solvent at 70°C under vacuum conditions, is liquid at 25°C. is preferred.
• the polysilsesquioxane (F-1) obtained by the above method can be used in the form of a composition containing an unreacted organosilicon compound.
• an organosilicon compound having an unsaturated group which will be described later, may be used in the form of a composition containing unreacted substances.
• a polysilsesquioxane polysilsesquioxane composition
• uniform coating becomes easier, and operation when building up a dental curable composition on a substrate Excellent in nature.
• a polysilsesquioxane composition that is liquid at 25° C., it is possible to suppress color tone change when coating a substrate, and to obtain more excellent lubricity durability.
• organosilicon compounds to be used include phenyltriethoxysilane, trimethoxy(phenylethyl)silane (1-phenylethyl, 2-phenylethyl mixture), (1E,4E)-1-(4-hydroxy-3,5 -dimethoxyphenyl)-5-(3,4,5-trimethoxyphenyl)-1,4-pentadien-3-one, trimethoxy(4-vinylphenyl)silane, trimethoxy(4-methoxyphenyl)silane, phenyltrimethoxy Organosilicon compounds having a phenyl group such as silane and benzyltriethoxysilane; Having an alkyl group such as methoxysilane, ethyltrimethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane, propyltrimethoxysilane, cyclopenty
• Organosilicon compounds trimethoxy(4-vinylphenyl)silane, vinyltrimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, 3-(triethoxysilyl)propyl methacrylate, allyltriethoxysilane, allyltrimethoxysilane, etc.
• organic silicon compounds having an unsaturated group of An organic silicon compound may be used individually by 1 type, and may mix 2 or more types. From the viewpoint of improving adhesion to ceramic substrates and improving affinity with the polymerizable compound (A) when combined with a filler (E) described later, an organosilicon compound having a phenyl group and an organosilicon compound having an unsaturated group. , and mixtures thereof are preferred, and phenyltriethoxysilane, 3-(trimethoxysilyl)propyl acrylate, and mixtures thereof are more preferred.
• the content of polysiloxane (F) improves the adhesion to the ceramic substrate, and the polymerizable compound (A) when combined with the filler (E).
• the total amount of the curable dental composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more.
• the hardness of the cured product it is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.
• the range may be a combination of any of these upper and lower limits.
• the content of polysiloxane (F) is, for example, preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, even more preferably 0.5 to 5% by mass.
• the curable dental composition used in the present invention may optionally contain solvents such as organic solvents, additives such as coloring agents (pigments), ultraviolet absorbers, and antioxidants to the extent that the effects of the present invention are not impaired. may be added as appropriate.
• the viscosity of the dental curable composition of the present invention is preferably 10 to 1000 mPa ⁇ s, more preferably 20 to 800 mPa ⁇ s, more preferably 40 to 600 mPa ⁇ s, from the viewpoint of operability such that it can be uniformly applied to a substrate. s is more preferred. Within this range, the curable composition can be easily applied to a desired area without dripping.
• the viscosity of the dental curable composition of the present invention can be measured, for example, with a Brookfield viscometer under conditions of 25° C. and 20 rpm.
• the pencil hardness of the cured film (cured product) of the curable dental composition of the present invention is preferably F or higher, more preferably H or higher, and even more preferably 2H or higher, from the viewpoint of abrasion resistance and impact resistance.
• the pencil hardness of the cured film can be measured according to JIS K 5600-5-4:1999, for example.
• the dental curable composition of the present invention is preferably used as a coating agent for coating a substrate. Therefore, the base material to be coated according to the present invention will be described.
• the base material can be selected from commonly available dental prosthesis materials.
• the substrate may be used alone or in combination of two or more.
• the substrate preferably contains at least one selected from the group consisting of zirconia, alumina, quartz glass, lithium silicate glass, acrylic resin, composite materials containing polymer resins and inorganic fillers, and may contain zirconia. more preferred.
• Zirconia contains zirconia as a main component and includes a zirconia sintered compact after sintering zirconia.
• a "main component” is a component that is contained in the largest amount, and is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• a zirconia sintered body is mainly sintered zirconia crystal grains. Therefore, in this specification, zirconia before sintering will be described, but unless otherwise stated, if there is no problem, "zirconia” can be read as “zirconia sintered body”. . And vice versa.
• the zirconia sintered body can contain zirconia and a stabilizer capable of suppressing the phase transition of zirconia (hereinafter also simply referred to as "stabilizer"). That is, the base material before sintering can contain zirconia and a stabilizer.
• the stabilizer examples include calcium oxide (CaO), magnesium oxide (MgO), yttrium oxide (Y 2 O 3 ), cerium oxide (CeO 2 ), scandium oxide (Sc 2 O 3 ), niobium oxide (Nb 2 O 5 ), lanthanum oxide (La 2 O 3 ), erbium oxide (Er 2 O 3 ), praseodymium oxide (Pr 6 O 11 , Pr 2 O 3 ), samarium oxide (Sm 2 O 3 ), europium oxide (Eu 2 O 3 ) and thulium oxide (Tm 2 O 3 ), with yttria being preferred.
• These stabilizers may be used singly or in combination of two or more.
• the content of the stabilizer in the zirconia of the present invention can be measured, for example, by inductively coupled plasma (ICP) emission spectrometry, X-ray fluorescence analysis (XRF), and the like.
• ICP inductively coupled plasma
• XRF X-ray fluorescence analysis
• the content of yttria is 3.0 to 7.5 mol% with respect to the total mol of zirconia and the stabilizer from the viewpoint of the strength and translucency of the sintered body. preferably 3.5 to 7.0 mol %, and even more preferably 4.0 to 6.5 mol %.
• the yttria content is 3.0 mol % or more, the translucency of the sintered body can be enhanced, and when it is 7.5 mol % or less, a decrease in strength of the sintered body can be suppressed.
• the content of calcium oxide is preferably 1 mol% or less, more preferably 0.3 mol% or less, based on a total of 100 mol% of zirconia and stabilizer. .
• the content of magnesium oxide is preferably 1 mol% or less, more preferably 0.3 mol% or less, based on a total of 100 mol% of zirconia and stabilizer. .
• the content of cerium oxide is preferably 1 mol% or less, more preferably 0.3 mol% or less, based on the total 100 mol% of zirconia and stabilizer. .
• Zirconia sintered bodies include not only sintered bodies obtained by sintering molded zirconia particles under normal pressure or under no pressure, but also high-temperature pressurization such as HIP (Hot Isostatic Pressing). Sintered bodies densified by processing are also included.
• HIP Hot Isostatic Pressing
• the zirconia sintered body preferably has at least one of partially stabilized zirconia and fully stabilized zirconia as a matrix phase.
• the main crystal phase of zirconia is at least one of tetragonal system and cubic system.
• Zirconia may contain both tetragonal and cubic crystal systems.
• the zirconia sintered body does not substantially contain a monoclinic system.
• Zirconia partially stabilized by adding a stabilizer is called partially stabilized zirconia (PSZ), and completely stabilized zirconia is called fully stabilized zirconia.
• the shape and size (dimensions) of the base material can be appropriately selected according to the application, the patient's oral environment, etc.
• the dental prosthesis of the present invention comprises a base material and a resin layer, wherein the resin layer comprises the polymerizable compound (A), the polyfunctional thiol (B-1), the fluorescent agent (C), and a polymerized cured product of a curable composition containing a polymerization initiator (D). Part or all of the base material is covered with the resin layer.
• the resin layer is obtained by coating the dental curable composition on the base material and polymerizing and curing the composition.
• the dental prosthesis of the present invention may have two or more resin layers with different compositions. Two or more resin layers can be laminated on the substrate.
• the thickness of the resin layer on the substrate is preferably 1 to 500 ⁇ m, more preferably 7 to 100 ⁇ m. , more preferably 7 to 80 ⁇ m, most preferably 7 to 50 ⁇ m.
• the thickness of the resin layer is preferably the thickness of the thickest portion.
• a substrate having a predetermined shape and dimensions is produced.
• a patient's dental prosthesis is made with the base material described above using known methods.
• a dental curable composition is applied to the substrate.
• an adhesive composition (G) separately prepared in advance is coated on the base material, if necessary.
• Application can be performed, for example, using a brush.
• the area of the base material to be coated with the dental curable composition can be appropriately selected according to the patient's oral environment.
• the area to which the dental curable composition is applied is preferably the area exposed in the oral cavity.
• the area to which the dental curable composition is applied may be the area facing the abutment tooth.
• the substrate coated with the dental curable composition is polymerized.
• Polymerization conditions can be, for example, 90 seconds using an irradiator emitting light in the wavelength range of 500 nm.
• the same steps can be repeated.
• the dental prosthesis of the present invention can be obtained by modifying the shape and polishing as necessary.
• an adhesive composition (G) containing an adhesive monomer (a-4) having an acidic group is adhered with an adhesive composition (G) containing an adhesive monomer (a-4) having an acidic group.
• a method of applying a dental curable composition is also preferably used.
• the volatile organic solvent (H) contained in the primer composition (G) preferably have a boiling point of 150° C. or lower, more preferably 100° C. or lower, at normal pressure. When a volatile organic solvent having a boiling point of over 150° C.
• Volatile organic solvents (H) include alcohols such as ethanol, methanol, 1-propanol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and diethyl ketone; 1,2-dimethoxyethane and 1,2-diethoxyethane.
• Ethers such as tetrahydrofuran
• Esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl
• (Meth)acrylic acid esters such as (meth)acrylates can be mentioned.
• (meth)acrylic acid esters are preferred because they can be cured simultaneously with the polymerizable monomer, and methyl methacrylate is particularly preferred because of its low toxicity and low boiling point.
• the volatile organic solvent (H) may be used singly or in combination of two or more as necessary.
• the content of the volatile organic solvent (H) is preferably 90 to 99.9% by mass, more preferably 95 to 99% by mass, based on the total amount of the primer composition (G) from the viewpoint of coatability (operability). , 97 to 99 mass % is more preferred.
• the dental prosthesis of the present invention can increase transparency and impart fluorescence compared to the base material alone. Moreover, the dental prosthesis of the present invention can maintain higher glossiness and fluorescence than the base material alone. As a result, the dental prosthesis of the present invention can have an appearance closer to that of natural teeth than the base alone.
• the present invention includes embodiments in which the above configurations are combined in various ways within the scope of the technical idea of the present invention as long as the effects of the present invention are exhibited.
• UV1700B Urethane acrylate oligomer (trade name “UV1700B” manufactured by Mitsubishi Chemical Corporation, viscosity at 25° C.: 40,000 to 100,000 mPa s, pencil hardness of cured film: 4H)
• UV1700B Urethane acrylate oligomer
• UA-306T Pentaerythritol triacrylate toluene diisocyanate urethane prepolymer (trade name “UA-306T” manufactured by Kyoeisha Chemical Co., Ltd.)
• SR454NS ethoxylated (3) trimethylolpropane triacrylate (Sartomer Company, Exton, PA, "SR454NS")
• SR9003NS propoxylated (2) neopentyl glycol diacrylate (“SR9003NS” from Sartomer Company, Exton, PA)
• DPHA dipentaerythritol hexaacrylate (“DPHA” from Sartomer Company, Exton, PA)
• U4TH N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate
• BAPO bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide
• Lucirin-TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
• CQ dl-camphorquinone
• Examples 1-34, Comparative Examples 1-7 A dental curable composition and a base material of each example and comparative example were prepared as follows, and their properties were evaluated. The results are shown in Tables 1-4.
• dental zirconia (trade name "KATANA (registered trademark) Ziroconia STML NW", thickness 14 mm, Kuraray Noritake Dental Co., Ltd.) was obtained in a hemispherical shape with a diameter of 12 mm, or A rectangular parallelepiped shape with a thickness of 2.4 mm, a length of 36 mm and a width of 24 mm, or a disc shape with a diameter of 22 mm and a thickness of 1.2 mm was cut by a dental cutting machine (trade name “DWX-51D”, Roland DG. (manufactured by Co., Ltd.) to produce a molded product.
• DWX-51D Roland DG.
• the molding is fired at 1550 ° C. for 2 hours using a firing furnace manufactured by SK Medical Electronics Co., Ltd. (trade name "Noritake Katana (registered trademark) F-1N”), and a hemisphere with a diameter of 10 mm is fired.
• the substrate is ultrasonically cleaned in acetone, dried, and coated on the substrate.
• a cuboidal or disk-shaped zirconia base material was prepared as a preparatory preparation for this.
• the angle of measurement was 60°.
• the glossiness is preferably 70% or more, more preferably 75% or more, and 80% or more, from the viewpoint of luster durability that can maintain gloss equivalent to that of natural teeth for a long period of time. is more preferable, and 85% or more is particularly preferable.
• the arithmetic mean roughness Ra is preferably 3.8 ⁇ m or less, more preferably 3.3 ⁇ m or less, even more preferably 2.8 ⁇ m or less, from the viewpoint of excellent wear resistance, and 2.3 ⁇ m The following are particularly preferred.
• Arithmetic mean roughness Ra may be, for example, 1.0 ⁇ m or more.
• surface roughness after abrasion represents arithmetic mean roughness Ra.
• the fluorescence intensity is preferably 120 to 6,000, more preferably 350 to 5,800, and even more preferably 550 to 5,500, from the viewpoint of fluorescence equivalent to that of natural teeth.
• Retention rate of fluorescence intensity (%) (fluorescence intensity after abrasion test/fluorescence intensity before abrasion test) x 100
• the fluorescence intensity before the abrasion test represents the fluorescence intensity calculated in the above "Evaluation of fluorescence of the polymerized and cured product of the curable dental composition”
• the fluorescence intensity after the abrasion test is the fluorescence intensity after the abrasion test.
• the fluorescence intensity calculated by the method described in "Evaluation of Fluorescence of Polymerized and Cured Dental Curable Composition" is shown.
• the retention rate of fluorescence intensity is preferably 80% or more, more preferably 85% or more, more preferably 90%, from the viewpoint of fluorescence durability that can maintain fluorescence equivalent to that of natural teeth for a long period of time. % or more, and particularly preferably 95% or more.
• Each prepared dental curable composition was applied and cured under the curing conditions shown in Tables 1 to 4 to obtain test pieces.
• the chromaticity of the test piece was measured in the same manner as the measurement of the chromaticity of the zirconia substrate described above, and these were defined as L * 1, a * 1, and b * 1.
• ⁇ E * ⁇ (L * 1-L * 0) 2+ (a * 1-a * 0) 2+ (b * 1-b * 0) 2 ⁇ 1/2
• the color difference ⁇ E * is preferably as small as possible from the viewpoint of influence on the color tone of the substrate.
• the color difference ⁇ E * is preferably 1.6 or less, more preferably 1.4 or less, still more preferably 1.2 or less, and most preferably 1.0 or less.
• Examples 1 to 34 were compared to Comparative Examples 2 to 7 in the lubricating durability and fluorescent durability of the cured product in tests assuming an oral environment. Furthermore, it was excellent in the effect of suppressing color tone change. In addition, Examples 1-34 were superior in operability as compared with Comparative Examples 2-4. Furthermore, Examples 1-34 were superior in wear resistance of the cured products compared to Comparative Examples 2-5. In addition, Examples 1 to 34 were superior to Comparative Examples 4 and 6 in fluorescence. Moreover, Comparative Example 1, which does not contain the fluorescent agent (C), did not exhibit fluorescence. Furthermore, Comparative Example 7, which does not contain the polymerizable compound (A), was not sufficiently cured, and each characteristic could not be evaluated.

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