WO2013038603A1 - Dérivé d'adamantane - Google Patents

Dérivé d'adamantane Download PDF

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WO2013038603A1
WO2013038603A1 PCT/JP2012/005332 JP2012005332W WO2013038603A1 WO 2013038603 A1 WO2013038603 A1 WO 2013038603A1 JP 2012005332 W JP2012005332 W JP 2012005332W WO 2013038603 A1 WO2013038603 A1 WO 2013038603A1
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meth
dental
bis
acid
salt
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PCT/JP2012/005332
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Japanese (ja)
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克樹 伊藤
大野　英俊
裕祐 高畑
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クラレノリタケデンタル株式会社
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Publication of WO2013038603A1 publication Critical patent/WO2013038603A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • 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 novel adamantane derivative. Since adamantane derivatives have unique properties such as high heat resistance, transparency, chemical resistance, and lubricity, they are used in various applications such as the pharmaceutical field, electronics field, various resin raw materials and dental applications.
  • the present invention also relates to an adamantane derivative particularly useful as a polymerizable monomer constituting a dental material.
  • Dental materials such as composite resin for dental filling, crown materials, dental adhesives, and dental cement are used to repair missing teeth.
  • a polymerizable monomer particularly a (meth) acrylic acid ester compound
  • a polymerizable monomer particularly a (meth) acrylic acid ester compound
  • examples thereof include bisphenol A glycidyl dimethacrylate (commonly known as Bis-GMA), 2,2-bis (4-methacryloyloxypoly) which incorporates an aromatic group having a rigid structure such as bisphenol A in the molecule as a spacer.
  • Bis-GMA bisphenol A glycidyl dimethacrylate
  • 2,2-bis (4-methacryloyloxypoly) which incorporates an aromatic group having a rigid structure such as bisphenol A in the molecule as a spacer.
  • Ethoxyphenyl) propane average number of added moles of ethoxy group: 2.6
  • D2.6E 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate
  • UDMA 2,2,4-trimethylhexamethylenebis (2-
  • resin dental materials containing the (meth) acrylic acid ester compounds as described above have come to be frequently used in dental treatment due to the increasing demand for aesthetics.
  • many metal materials are still used in parts that receive a very strong occlusal force, such as the occlusal surface of the molars. This is not only an aesthetic aspect, but also because it avoids metal allergies. Development of strong resin-based dental materials is desired.
  • Bis-GMA has been widely used as a (meth) acrylic acid ester compound that enhances the strength of resin-based materials, but Bis-GMA has a high viscosity, so a dental filling composite containing Bis-GMA Resin pastes are hard and sticky, and dental adhesives have problems such as poor conformability to the tooth structure when applied to the tooth surface, which impairs operability.
  • D2.6E or UDMA which has a low viscosity, has been often used to adjust the paste operability.
  • a composite resin machine for dental filling can be used. There was room for improvement because the mechanical strength decreased.
  • an adamantane derivative represented by the following formula (1) is provided. (Wherein R 1 to R 5 are each hydrogen or a methyl group, m is an integer of 0 to 10, and n is an integer of 1 to 10)
  • the present invention is a dental composition containing the adamantane derivative.
  • the present invention is a dental composite resin, a dental adhesive, a dental cement, and a dental primer using the dental composition.
  • an adamantane derivative capable of increasing mechanical strength and imparting good operability when applied to a dental material
  • a dental composition having high mechanical strength and excellent operability and a dental material using the dental composition can be provided.
  • the adamantane derivative of the present invention is represented by the following formula (1).
  • R 1 to R 5 are each hydrogen or a methyl group.
  • m is an integer of 0 to 10, preferably 0 to 4.
  • n is an integer of 1 to 10, preferably 2 to 6.
  • the adamantane derivative of the present invention can be synthesized, for example, by reacting an adamantane represented by the following formula (2) with a (meth) acrylate having an isocyanate group represented by the following formula (3). (Wherein R 1 to R 5 , m and n are the same as those in the above formula (1).)
  • Examples of the adamantane represented by the above formula (2) include 1,3-adamantanediol, 2,4-adamantanediol, 1,4-adamantanediol, 1,3-adamantane dimethanol, and 2,4-adamantane dimethanol.
  • Examples of (meth) acrylates represented by the above formula (3) include 2-acryloyloxymethyl isocyanate, 2-methacryloyloxymethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate and the like.
  • amines and organometallic compounds can be used as the catalyst.
  • amines include triethylamine, tributylamine, trioctylamine and the like.
  • organometallic compound an organometallic compound having catalytic activity for the urethanization reaction can be used. Specific examples include organic cobalt compounds such as cobalt naphthenate, and organic tin compounds such as tetra-n-butyltin, trimethyltin hydroxide, dimethyltin dichloride, di-n-butyltin dilaurate, and tin octoate. it can.
  • the amount of the catalyst used is usually preferably about 0.01 to 10 mol, particularly preferably 0.01 to 5 mol, per 1 mol of adamantane as a raw material.
  • the usage-amount of a catalyst is less than 0.01 mol, there exists a possibility that the efficiency of a catalyst may fall and reaction time may become long. On the other hand, if it exceeds 10 mol, the effect due to the increase in the amount used cannot be obtained.
  • the amount of the catalyst used is 5 mol or less, the balance between the effect of the catalyst and the economical efficiency becomes good.
  • the reaction may be carried out in a solvent-free system or using a solvent.
  • a solvent in which the solubility of adamantane is preferably 0.5% by mass or more, more preferably 10% by mass or more can be used.
  • Specific examples include hexane, heptane, toluene, dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), ethyl acetate, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), and the like. It is done. From the viewpoint of reaction time, DMF and DMSO are preferred.
  • a solvent may be used individually by 1 type and may be used in combination of 2 or more type.
  • the solvent is preferably used so that the concentration of adamantane in the reaction system is 0.5% by mass or more. More preferably, it is 10 mass% or more.
  • the adamantane may be in a suspended state in the solvent, but it is preferably dissolved.
  • the reaction temperature between adamantanes and (meth) acrylates is usually preferably about 0 to 150 ° C., more preferably 20 to 100 ° C. If the temperature is too low, the reaction rate decreases and the reaction time becomes longer. When the reaction temperature is 0 ° C. or higher, the reaction rate does not decrease and the reaction time is shortened. On the other hand, when the reaction temperature is higher than 150 ° C., the product becomes intensely colored. If reaction temperature is 100 degrees C or less, a product with little coloring can be obtained.
  • the pressure during the reaction is preferably about 0.01 to 10 MPa in absolute pressure, more preferably normal pressure to 1 MPa. If the pressure is too high, there is a safety problem and a special device is required, which is not industrially useful. When the pressure is 10 MPa or less, safety is ensured, so that no special device is required, which is industrially useful.
  • the reaction time is usually preferably about 1 minute to 24 hours, more preferably 1 to 15 hours.
  • the target product after completion of the reaction, the target product may be purified by distillation, crystallization, column separation or the like.
  • the purification method can be selected depending on the properties of the product and the type of impurities.
  • Examples of the adamantane derivative of the present invention include those shown in the chemical formula below.
  • the dental composition of the present invention contains the adamantane derivative of the present invention described above. About components other than an adamantane derivative, what is necessary is just to select suitably according to the use of a dental composition.
  • the dental composition is, for example, a dental composition containing a polymerizable monomer (especially a (meth) acrylic acid ester compound), and a part or all of the known polymerizable monomer is substituted with the above adamantane derivative.
  • the configuration may be replaced with.
  • component (A) examples include, for example, a polymerizable compound having one polymerizable group and one or more hydroxyl groups.
  • Monomer (B), polymerizable monomer component having acidic group (C), polymerizable monomer component such as crosslinkable polymerizable monomer (D), and polymerization initiator (E), polymerization acceleration An agent (F), a filler (G), a solvent (H), etc. are mentioned.
  • total amount of polymerizable monomer component indicates the total weight of the adamantane derivative (A) and the polymerizable monomers (B) to (D).
  • the blending amount of the adamantane derivative (A) may be appropriately determined according to the use of the dental composition.
  • the adamantane derivative (A) is 10 to 95 masses. It is preferable that a part is contained.
  • the mechanical strength is high, or the penetration of the dentin into the collagen layer is good, It has the advantage of high adhesive strength.
  • the blending amount of the adamantane derivative (A) is less than 10 parts by mass, sufficient mechanical strength may not be obtained, or the adhesive strength may decrease and the adhesive durability may decrease.
  • the blending amount of the adamantane derivative (A) exceeds 95 parts by mass, the operability may be deteriorated, or the decalcification may be insufficient, and sufficient adhesive strength may not be obtained. It is below mass parts.
  • the terms “monofunctional”, “bifunctional” and “trifunctional” are used, and “monofunctional”, “bifunctional” and “trifunctional” It represents having one, two and three polymerizable groups in the molecule, respectively.
  • This polymerizable group is a vinyl group or a radical copolymerizable group.
  • the dental composition of the present invention may contain a polymerizable monomer (B) having one polymerizable group and one or more hydroxyl groups.
  • a polymerizable monomer (B) having one polymerizable group and one or more hydroxyl groups.
  • the adhesive strength is good.
  • the polymerizable monomer (B) has a polymerizable group, radical polymerization becomes possible and copolymerization with other monomers becomes possible.
  • the polymerizable monomer (B) having one polymerizable group and one or more hydroxyl groups is not particularly limited.
  • the polymerizable group is a vinyl group or a radical copolymerizable group. From the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth) acryl group or a (meth) acrylamide group.
  • the polymerizable monomer (B) is preferably used as a component of the dental composition.
  • the polymerizable group since the oral cavity is a moist environment, there is a possibility that the polymerizable group may be eliminated by hydrolysis or the like.
  • the polymerizable group is preferably a methacryl group or a methacrylamide group.
  • the polymerizable monomer (B) has one or more hydroxyl groups, has good hydrophilicity, and is a monofunctional polymer monomer having one polymerizable group, so that an adamantane derivative (When the composition of the present invention containing A) and the polymerizable monomer (B) is used as a dental composition, there is an effect that the permeability of dentin into the collagen layer is further improved.
  • Examples of such a polymerizable monomer (B) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth).
  • Acrylate 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide and the like can be mentioned.
  • 2-hydroxyethyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, 3 -Hydro Shipuropiru (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate preferably, particularly preferably 2-hydroxyethyl methacrylate.
  • the blending amount of the polymerizable monomer (B) is not particularly limited, but is 5 to 90 parts by mass of the polymerizable monomer (B) with respect to 100 parts by mass of the total amount of the polymerizable monomer component. It is preferable to become.
  • a composition in which the blending amount of the polymerizable monomer (B) is in such a range is used as a dental composition, the penetration of dentin into the collagen layer is good and the adhesive strength is good. Therefore, it is preferable.
  • the blending amount of the polymerizable monomer (B) is less than 5 parts by mass, the contribution of the penetration of the dentin into the collagen layer by the polymerizable monomer (B) may not be obtained, and the adhesive strength is low. May decrease.
  • the compounding amount of the polymerizable monomer (B) is more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more.
  • the blending amount of the polymerizable monomer (B) is more preferably 80 parts by mass or less, further preferably 75 parts by mass or less, and particularly preferably 70 parts by mass or less.
  • the dental composition of the present invention may contain a polymerizable monomer (C) having an acidic group.
  • the polymerizable monomer (C) having an acidic group is not particularly limited, but a monofunctional polymerizable monomer having one carboxyl group or its acid anhydride group in the molecule, and a plurality of monomers in the molecule.
  • Monofunctional polymerizable monomer having carboxyl group or acid anhydride group thereof, monofunctional polymerizable monomer having phosphinicooxy group or phosphonooxy group in the molecule (monofunctional radical polymerizable phosphate ester) May be called).
  • Examples of monofunctional polymerizable monomers having one carboxyl group or acid anhydride group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloyl asparagine Acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate , 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl -P-aminobenzoic acid, N- (
  • Examples of monofunctional polymerizable monomers having a plurality of carboxyl groups or acid anhydride groups in the molecule include 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyl Oxydecane-1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 2- (meth) acryloyloxyethyl -3'-methacryloyloxy-2 '-(3,4-dicarboxybenzoyloxy) propyl succinate, 4- (2- (meth) acryloyloxyethyl) trimellitate anhydride, 4- (2- (meth) (Acryloyloxyethyl) trimellitate, 4- (meth) acryloyloxyethyl trimellitate,
  • Examples of monofunctional polymerizable monomers having a phosphinicooxy group or phosphonooxy group in the molecule include 2- (meth) acryloyloxyethyl Dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 2- (Meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2- (meth) acrylamidoethyl dihydrogen phosphate, bis (6- (meth) acryloyloxyhexyl) hydrogen phosphate, bis (10- Meth) acryloyloxydecyl) hydrogen phosphate, bis ⁇ 2- (meth) acryloyloxy - (1-hydroxymethyl
  • monofunctional polymerizable monomers having an acidic group such as 2- (meth) acrylamido-2-methylpropanesulfonic acid, 10-sulfodecyl (meth) acrylate, etc. And other monomers.
  • the dental composition of the present invention may contain 1 to 70 parts by mass of the polymerizable monomer (C) having an acidic group in 100 parts by mass of the total amount of the polymerizable monomer components.
  • the polymerizable monomer (C) having an acidic group itself is Since it has an acid etching effect and a primer treatment effect, it has an advantage that a pretreatment such as an acid etching treatment and a primer treatment is not required.
  • a dental adhesive that is simple, has high adhesive strength, and has good adhesion durability, particularly preferably a one-component dental adhesive.
  • a dental adhesive that is simple, has high adhesive strength, and has good adhesion durability, particularly preferably a one-component dental adhesive.
  • the compounding amount of the polymerizable monomer (C) having an acidic group is less than 1 part by mass, the acid etching effect or the primer treatment effect may not be obtained, more preferably 2 parts by mass or more, The amount is preferably 5 parts by mass or more.
  • the compounding amount of the polymerizable monomer (C) having an acidic group exceeds 50 parts by mass, sufficient curability may not be obtained, and the adhesive performance may be deteriorated, and more preferably 60 masses. Part or less, and more preferably 50 parts by weight or less.
  • the dental composition of the present invention may have a crosslinkable polymerizable monomer (D).
  • a crosslinkable polymerizable monomer (D) An aromatic compound type bifunctional polymerizable monomer, an aliphatic compound type bifunctional polymerizable monomer, trifunctionality
  • the above polymerizable monomers are exemplified.
  • aromatic compound-based bifunctional polymerizable monomers examples include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (commonly referred to as “Bis-GMA”), 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) ) Propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane), 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (Meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyv Nyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl)
  • Examples of aliphatic compound-based bifunctional polymerizable monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate (commonly called “3G”), propylene glycol Di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane and 2,2 , 4-Trimethyl Hexamethylene bis (2-carbamoyloxyethyl) dimethacryl
  • trifunctional or higher polymerizable monomers examples include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) And bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like. .
  • the dental composition of the present invention may contain 5 to 90 parts by mass of the crosslinkable polymerizable monomer (D) in 100 parts by mass of the total amount of the polymerizable monomer components.
  • the mechanical strength or the adhesive strength is further improved.
  • the amount of the crosslinkable polymerizable monomer (D) is less than 5 parts by mass, sufficient mechanical strength or adhesive strength may not be obtained, and more preferably 10 parts by mass or more. More preferably, it is 15 parts by mass or more.
  • the amount of the crosslinkable polymerizable monomer (D) exceeds 90 parts by mass, the operability is deteriorated, or the penetration of the dentin into the collagen layer is insufficient, and high adhesive strength is obtained. There is a possibility that it may become impossible, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less.
  • the dental composition of the present invention may contain a polymerizable monomer other than the above (A), (B), (C) and (D) as necessary.
  • the polymerization initiator (E) used in the present invention can be selected from polymerization initiators used in the general industry, and among them, polymerization initiators used for dental use are preferably used. In particular, polymerization initiators for photopolymerization and chemical polymerization are used singly or in appropriate combination of two or more.
  • Photopolymerization initiators include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, ⁇ -diketones, coumarins, anthraquinones, benzoin alkyls Examples include ether compounds and ⁇ -aminoketone compounds.
  • 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, benzoyldi- (2,6-dimethylphenyl) phosphonate and the like.
  • bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichloro).
  • Benzoyl) -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, ( 2 5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide and the like.
  • the water-soluble acylphosphine oxides used as the photopolymerization initiator preferably have an alkali metal ion, alkaline earth metal ion, pyridinium ion or ammonium ion in the acylphosphine oxide molecule.
  • water-soluble acyl phosphine oxides can be synthesized by the method disclosed in European Patent No. 0009348 or JP-A-57-197289.
  • water-soluble acylphosphine oxides include monomethylacetylphosphonate / sodium, monomethyl (1-oxopropyl) phosphonate / sodium, monomethylbenzoylphosphonate / sodium, monomethyl (1-oxobutyl) phosphonate / sodium, Monomethyl (2-methyl-1-oxopropyl) phosphonate / sodium, acetylphosphonate / sodium, monomethylacetylphosphonate / sodium, acetylmethylphosphonate / sodium, methyl 4- (hydroxymethoxyphosphinyl) -4 -Oxobutanoate sodium salt, methyl-4-oxophosphonobutanoate mononatrium salt, acetyl phenyl phosphinate sodium salt, (1-o Sopropyl) pentylphosphinate sodium, methyl-4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetyl
  • acylphosphine oxides and water-soluble acylphosphine oxides 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6 -Trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.
  • Examples of the thioxanthones or quaternary ammonium salts of thioxanthones used as the photopolymerization initiator include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy-9H- Thioxanthen-4-yloxy) -N, N, N-trimethyl-propaneaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- ( 3,4-Dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-tri Tyl-1-propaneaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9H-
  • thioxanthones or quaternary ammonium salts of thioxanthones a particularly preferred thioxanthone is 2-chlorothioxanthen-9-one, and a particularly preferred quaternary ammonium salt of thioxanthones is 2 -Hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride.
  • ketals used as the photopolymerization initiator include benzyl dimethyl ketal and benzyl diethyl ketal.
  • Examples of the ⁇ -diketone used as the photopolymerization initiator include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′- Examples thereof include oxybenzyl and acenaphthenequinone.
  • camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.
  • Examples of coumarin compounds used as the photopolymerization initiator include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, and 3-benzoyl-5.
  • 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly preferable.
  • anthraquinones used as the photopolymerization initiator include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1 -Hydroxyanthraquinone and the like.
  • a dental composition having excellent photocurability in the visible and near-ultraviolet regions and having sufficient photocurability can be obtained using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.
  • a light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.
  • an organic peroxide is preferably used as the chemical polymerization initiator.
  • the organic peroxide used for said chemical polymerization initiator is not specifically limited, A well-known thing can be used.
  • Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.
  • hydroperoxide used as the chemical polymerization initiator examples include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide. It is done.
  • diacyl peroxide used as the chemical polymerization initiator examples include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and 2,4-dichlorobenzoyl. Examples thereof include peroxide and lauroyl peroxide.
  • dialkyl peroxide used as the chemical polymerization initiator examples include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide).
  • Examples of the peroxyketal used as the chemical polymerization initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester, etc. Can be mentioned.
  • peroxyester used as the chemical polymerization initiator examples include ⁇ -cumyl peroxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentyl.
  • Peroxy-2-ethylhexanoate t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t- Examples include butyl peroxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. It is done.
  • peroxydicarbonate used as the chemical polymerization initiator examples include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, and diisopropyl. Examples thereof include peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate and diallyl peroxydicarbonate.
  • diacyl peroxide is preferably used from the comprehensive balance of safety, storage stability, and radical generating ability, and benzoyl peroxide is particularly preferably used among them.
  • the compounding quantity of the polymerization initiator (E) used for this invention is not specifically limited, From viewpoints, such as sclerosis
  • the blending amount of the polymerization initiator (E) exceeds 30 parts by mass, when the polymerization performance of the polymerization initiator itself is low, sufficient mechanical strength cannot be obtained, or sufficient adhesive strength is obtained. There is a possibility that it may not be obtained, and further, there is a possibility that precipitation from the composition may be caused, so the amount is more preferably 20 parts by mass or less.
  • the above polymerization initiator (E) is used together with a polymerization accelerator (F).
  • a polymerization accelerator (F) used in the present invention, amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiols Compounds and the like.
  • the amines used as the polymerization accelerator (F) are classified into aliphatic amines and aromatic amines.
  • the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate , Tertiary fats such as triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Amine
  • aromatic amine examples include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, and N, N-bis. (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl)- 3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl
  • At least one selected from the group consisting of dimethylaminobenzoic acid n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone is preferably used.
  • Examples of the sulfinic acid and salts thereof used as the polymerization accelerator (F) include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluenesulfin.
  • Acid calcium benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, Potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzene Zensulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate Calcium, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesul
  • the borate compound used as the polymerization accelerator (F) is preferably an aryl borate compound.
  • aryl borate compounds include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluoro) as borate compounds having one aryl group in one molecule.
  • borate compounds having two aryl groups in one molecule include dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5-bistrifluoromethyl) phenyl.
  • dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitro Phenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) Boron and Sodium salt, lithium salt, potassium salt of alkyldi (m-octyloxyphenyl) boron (wherein the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dode
  • borate compounds having three aryl groups in one molecule include monoalkyltriphenyl boron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3 , 5-Bistrifluoromethyl) phenyl boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltri ( p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butyloxyphenyl) Boron, monoalkyltri (m-butyloxyphenyl) boron, monoa Kirtri (p-o
  • borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenyl boron.
  • aryl borate compounds it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability.
  • These aryl borate compounds may be used alone or in combination of two or more.
  • Barbituric acid derivatives used as the polymerization accelerator (F) include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butyl Barbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1 , 3-Dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3 -Dimethyl-5-cyclohexyl barbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohex Ru-1-ethy
  • barbituric acid derivatives include 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, And sodium salts of these barbituric acids.
  • Examples of the triazine compound used as the polymerization accelerator (F) include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,
  • 2,4,6-tris (trichloromethyl) -s-triazine is particularly preferred in terms of polymerization activity, and 2-phenyl-4 is preferred in terms of storage stability.
  • the copper compound used as the polymerization accelerator (F) for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.
  • Examples of the tin compound used as the polymerization accelerator (F) include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. It is done. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.
  • the vanadium compound used as the polymerization accelerator (F) is preferably IV-valent and / or V-valent vanadium compounds.
  • IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1- Japanese Patent Application Laid-Open Publication No.
  • halogen compound used as the polymerization accelerator (F) examples include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like. Are preferably used.
  • aldehydes used as the polymerization accelerator (F) include terephthalaldehyde and benzaldehyde derivatives.
  • the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Among these, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.
  • Examples of the thiol compound used as the polymerization accelerator (F) include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.
  • the compounding quantity of the polymerization accelerator (F) used for this invention is not specifically limited, From viewpoints, such as sclerosis
  • the blending amount of the polymerization accelerator (F) exceeds 30 parts by mass, when the polymerization performance of the polymerization initiator itself is low, sufficient mechanical strength cannot be obtained, or sufficient adhesive strength is obtained. There is a possibility that it may not be obtained, and further, there is a possibility that precipitation from the composition may be caused, so the amount is more preferably 20 parts by mass or less.
  • a filler (G) to the dental composition of the present invention.
  • Such fillers are generally roughly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers.
  • the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, and polystyrene.
  • the shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. From the viewpoints of handleability and mechanical strength of the resulting composition, the average particle size of the organic filler is preferably 0.001 to 50 ⁇ m, and more preferably 0.001 to 10 ⁇ m.
  • Inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, ytterbium fluoride, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium Glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass Etc.
  • the shape of the inorganic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle size of the inorganic filler is preferably 0.001 to 50 ⁇ m, and more preferably 0.001 to 10 ⁇ m.
  • the shape of the inorganic filler includes an amorphous filler and a spherical filler. From the viewpoint of improving the mechanical strength of the composition, it is preferable to use a spherical filler as the inorganic filler. Furthermore, when the spherical filler is used, there is an advantage that a composite resin having excellent surface lubricity can be obtained when the dental composition of the present invention is used as a dental composite resin.
  • the spherical filler is a particle diameter in a direction perpendicular to the maximum diameter, in which a photograph of the filler is taken with a scanning electron microscope (hereinafter abbreviated as SEM), and the particles observed in the unit field of view are rounded.
  • the average particle diameter of the spherical filler is preferably 0.1 to 5 ⁇ m. When the average particle size is less than 0.1 ⁇ m, the filling rate of the spherical filler in the composition is lowered, and the mechanical strength may be lowered. On the other hand, when the average particle diameter exceeds 5 ⁇ m, the surface area of the spherical filler is reduced, and a cured product having high mechanical strength may not be obtained.
  • the inorganic filler may be used after surface treatment with a known surface treatment agent such as a silane coupling agent as necessary.
  • a known surface treatment agent such as a silane coupling agent
  • the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane.
  • the organic-inorganic composite filler used in the present invention is obtained by previously adding a monomer compound to the above-described inorganic filler, forming a paste, polymerizing, and pulverizing.
  • TMPT filler trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized
  • the shape of the organic-inorganic composite filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 ⁇ m, and more preferably 0.001 to 10 ⁇ m. .
  • the filler Since the smaller the difference between the refractive index of the filler and the refractive index of the polymer component, the higher the transparency, the filler has a refractive index of 1.5 to 1.7, more preferably 1.55 to 1.65, It is particularly preferable to use one having a viscosity of 1.55 to 1.60.
  • Particularly preferable fillers from the viewpoint of aesthetics include barium glass, lanthanum glass, ytterbium fluoride and the like.
  • the blending amount of the filler (G) used in the present invention is not particularly limited, and the filler (G) is preferably 1 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer components. Since the suitable compounding amount of the filler (G) varies greatly depending on the embodiment to be used, a filler (corresponding to each embodiment is described in conjunction with the description of specific embodiments of the dental composition of the present invention described later). A suitable blending amount of G) will be shown.
  • the dental composition of the present invention preferably contains a solvent (H) depending on its specific embodiment.
  • the solvent include water (I), an organic solvent (J), and a mixed solvent thereof.
  • the dental composition of the present invention contains water (I), it exhibits excellent adhesive strength and excellent adhesive durability.
  • the content of water (I) is preferably 6 to 2000 parts by mass of water (I) with respect to 100 parts by mass of the total amount of polymerizable monomer components. When the content of water (I) is less than 6 parts by mass, the monomer permeability to the collagen layer becomes insufficient, and the adhesive strength may be reduced. On the other hand, when content of water (I) exceeds 2000 mass parts, there exists a possibility that the polymerizability of a monomer may fall, adhesive strength may fall, and adhesive durability may fall.
  • the content of water (I) is more preferably 7 parts by mass or more, and further preferably 10 parts by mass or more. Moreover, as for content of water (I), it is more preferable that it is 1500 mass parts or less. It is preferable that water (I) does not contain impurities that have an adverse effect, and distilled water or ion exchange water is preferable.
  • the organic solvent (J) examples include methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, hexane, toluene, chloroform, ethyl acetate, butyl acetate and the like.
  • the organic solvent (J) is preferably a water-soluble organic solvent, specifically, ethanol or acetone is Preferably used.
  • Content of the said organic solvent (J) is not specifically limited, Depending on embodiment, there exists a thing which does not require the mixing
  • the organic solvent (J) is preferably contained in an amount of 1 to 2000 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer components. Since the suitable compounding amount of the organic solvent (J) varies greatly depending on the embodiment to be used, it depends on each embodiment in conjunction with the description of specific embodiments of the dental composition of the present invention described later. A suitable blending amount of the organic solvent (J) will be shown.
  • the dental composition of the present invention may be blended with a polymerization inhibitor, an ultraviolet absorber, a thickener, a colorant, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not impaired.
  • the dental composition of the present invention includes a dental composite resin, a dental adhesive, a dental cement (resin cement, glass ionomer cement, resin reinforced glass ionomer cement), a dental primer, a foveal fissure filling material, and a denture. It can be used for a dental material such as a floor resin, and among them, it is preferably used as a dental composite resin, a dental adhesive, a dental cement, and a dental primer. These dental materials using the dental composition of the present invention have high mechanical strength and good operability. Moreover, the dental composition of this invention can also be used as an artificial tooth and a resin block for CAD / CAM produced by hardening
  • MIBK methyl isobutyl ketone
  • water methyl isobutyl ketone
  • A an adamantane derivative represented by the formula (A) (yellowish white solid, yield 60 g, yield 82%, melting point 88 ° C.).
  • Test Example 1 (Mechanical strength evaluation / bending strength measurement) The dental composition is filled in a mold (2 mm ⁇ 2 mm ⁇ 25 mm), and light irradiation (20 seconds ⁇ 5 times each on the front and back) is performed using a dental visible light irradiation machine (JET Light 3000, manufactured by Morita). A test piece was prepared. The test piece was immersed in 37 ° C. water for 24 hours, and the bending strength was measured by a three-point bending test method using a universal testing machine (manufactured by Instron) at a crosshead speed of 1 mm / min. As the mechanical strength, a bending strength of 80 MPa or more was judged good.
  • JET Light 3000 manufactured by Morita
  • the dental composition containing the adamantane derivative produced in Example 1 can obtain sufficient mechanical strength and excellent operability.
  • the dental composition containing Bis-GMA has a sufficient mechanical strength but is inferior in operability.
  • the dental composition containing D2.6E or UDMA is excellent in operability but has low mechanical strength.
  • the adamantane derivative of the present invention is suitable as a polymerizable monomer used for dental materials such as dental composite resins, dental adhesives, dental cements, and dental primers.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dental Preparations (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un dérivé d'adamantane représenté par la formule (1), qui est un monomère polymérisable qui, lorsqu'il est utilisé dans un produit dentaire, permet d'augmenter la résistance mécanique du produit dentaire et permet de conférer une bonne aptitude à la manipulation du produit dentaire. (Dans la formule R1 à R5 représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle ; m représente un nombre entier de 0 à 10 ; et n représente un nombre entier de 1 à 10). Une composition dentaire contenant le dérivé d'adamantane est utile comme produit dentaire tel qu'une résine composite dentaire, une substance adhésive dentaire, un ciment dentaire et une couche primaire dentaire.
PCT/JP2012/005332 2011-09-12 2012-08-24 Dérivé d'adamantane WO2013038603A1 (fr)

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CN108298922A (zh) * 2018-05-06 2018-07-20 段宝荣 一种建筑高强度灌浆料及其制备方法

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JP7104510B2 (ja) * 2017-11-29 2022-07-21 クラレノリタケデンタル株式会社 脂環式（メタ）アクリル化合物を含む硬化性組成物
CN108546036A (zh) * 2018-05-06 2018-09-18 段宝荣 含铬革屑改性建筑水泥灌浆料及其制备方法

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