Classifications

• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/70—Preparations for dentistry comprising inorganic additives
  • A61K6/71—Fillers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
  • A61K6/871—Quartz; SiO2
• • 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
  • A61C13/0003—Making bridge-work, inlays, implants or the like
  • A61C13/0022—Blanks or green, unfinished dental restoration parts

Definitions

• the present invention is a dental restoration curable composition preferably used as a dental material that can replace a part or the whole of a natural tooth, particularly a dental composite resin, in the field of dentistry.
• the present invention relates to a dental composite resin composed of a dental composite resin and a dental mill blank composed of a cured product of the curable composition for dental restoration.
• a dental restoration curable composition composed of a polymerizable monomer, an inorganic filler, a polymerization initiator and the like is called a dental composite resin, and is used today as a material for repairing tooth defects and caries. It is the most frequently used dental material.
• Dental composite resins have sufficient mechanical strength to replace natural teeth in cured products after polymerization and curing, water resistance to withstand long-term oral restoration, and polishability to obtain gloss equivalent to that of natural teeth. In the past state before polymerization and curing, it is required to have operability suitable for filling the tooth cavity using a dental instrument or the like.
• Patent Document 1 a technique for blending a polycarbonate dimethacrylate represented by the following formula (III) has been proposed for the purpose of realizing excellent paste operability and abrasion resistance of a cured product.
• Patent Document 2 a photocurable resin composition containing a polycarbonate containing at least two (meth) acrylate groups in a molecule having a molecular weight of 200 to 10,000 has been proposed (Patent Document 2).
• the operability at the time of manufacturing the cast clasp is excellent, the surface characteristics are excellent, and the deformability can be suppressed.
• A is an alkylene group having 1 to 6 carbon atoms
• R is an alkylene group having 2 to 5 carbon atoms having at least two carbon atoms in its backbone
• n is an integer of 1 to 4 carbon atoms. .. ]
• dental mill blanks are materials used for manufacturing dental prostheses such as inlays and crowns by a CAD / CAM system designed by a computer and cut by a milling device, and have been in demand in recent years. It is increasing rapidly.
• a dental mill blank a block body having a shape such as a rectangular parallelepiped, a cylinder, or a disk having an appropriate size is supplied, and this is set in a cutting machine and machined to restore the crown shape or dentition shape. Get things.
• various materials such as glass ceramics, zirconia, titanium, acrylic resin, composite materials including polymer resin and inorganic filler have been proposed.
• Dental mill blanks are also required to have sufficient mechanical strength to replace natural teeth, water resistance to withstand long-term oral restoration, and polishability to obtain luster equivalent to that of natural teeth.
• an inorganic filler is press-molded to obtain a molded product, and then a polymerizable monomer is immersed in the molded product to heat-polymerize the dental mill blank.
• Patent Document 3 By this manufacturing method, nanoparticles can be packed at a high density, and a dental mill blank having excellent mechanical strength and polishability can be obtained.
• Patent Document 1 has a problem of low mechanical strength and water resistance. There was also room for improvement in the operability of the paste.
• the dental curable composition disclosed in Patent Document 2 does not contain an inorganic filler, and the operability of the paste when used as a dental composite resin is very poor, and the obtained cured product is obtained. There was a problem that the durability of the resin was poor.
• the dental mill blank disclosed in Patent Document 3 has room for further improvement in toughness (breaking energy), mechanical strength, and water resistance.
• the mechanical strength particularly the bending strength
• the toughness decreases as the content of the inorganic filler increases, and the inorganic filler is filled. It was known that there is a trade-off relationship between mechanical strength (especially bending strength) and toughness because it is excellent when the content of the material is low (dental materials / instruments Vol.7 No.5 756-768). , 1988).
• the present invention has been made to solve the above-mentioned problems of the prior art, and the cured product has high mechanical strength and toughness, and has excellent water resistance and slip resistance for dental restoration. It is an object of the present invention to provide a composition. Another object of the present invention is to provide a dental restoration curable composition having excellent paste operability and a dental composite resin comprising the dental restoration curable composition. Further, it is an object of the present invention to provide a dental mill blank which has excellent aesthetics because it has few bubbles.
• the present invention includes the following inventions.
• It has at least one polymer structure selected from the group consisting of polycarbonate, polyarylate, and aromatic polysulfone, and the terminal hydroxy residue derived from the repeating unit constituting the polymer structure is directly (meth) acryloylated.
• a curable composition for dental restoration containing an inorganic filler (C) having an average primary particle size of 0.01 to 5 ⁇ m, and a polymerization initiator (D).
• R 1 and R 2 are independent groups represented by the following general formula (i) or groups represented by the general formula (ii), and X is a divalent group having 1 to 6 carbon atoms. It is a hydrocarbon group or an oxygen atom.
• R 3 and R 5 are independently divalent hydrocarbon groups having 1 to 10 carbon atoms
• R 4 and R 6 are independently hydrogen atoms or methyl groups, respectively, and k and l. Are independently integers from 0 to 6)
• the present invention it is possible to provide a curable composition for dental restoration, in which the cured product has high mechanical strength and toughness, and is excellent in water resistance and slipping durability. Further, the curable composition for dental restoration of the present invention is also excellent in operability of the paste. Further, the curable composition for dental restoration of the present invention is excellent in aesthetics of the cured product because it can suppress bubbles generated in the cured product. Further, according to the present invention, even when the content of the inorganic filler is large (for example, 50 to 95% by mass in the total amount of the curable composition for dental restoration), the cured product has high mechanical strength and toughness. It is possible to provide a curable composition for dental restoration, which has excellent water resistance and smoothness durability.
• the upper limit value and the lower limit value of the numerical range can be appropriately combined. Further, in the present specification, the numerical values of the respective symbols in the formula can be appropriately combined.
• the curable composition for dental restoration of the present invention is in one molecule of a specific (meth) acrylic acid ester compound (A) (hereinafter, may be simply referred to as “(meth) acrylic acid ester compound (A)”).
• a (meth) acrylic acid ester compound (B) having two or more (meth) acryloyloxy groups, an inorganic filler (C) having an average primary particle size of 0.01 to 5 ⁇ m, and a polymerization initiator (D). include.
• the (meth) acrylic acid ester compound (A) has at least one polymer structure selected from the group consisting of polycarbonate, polyarylate, and aromatic polysulfone, and the polymer. It is important that the terminal hydroxy residues from the repeating units that make up the structure are directly (meth) acryloylated compounds.
• the curable composition for dental restoration is a composition generally containing an inorganic filler and a (meth) acrylic acid ester compound as a polymerizable monomer, and a machine such as bending strength and elastic modulus of the obtained cured product. Many have excellent target strength.
• the polymer of the (meth) acrylic acid ester compound has low flexibility and is relatively fragile, and further, the fragility increases due to the increase in hardness due to the addition of the inorganic filler, so that the curable composition for dental restoration
• the "destructive energy” which is the total energy applied until the cured product of the object is destroyed, is reduced, that is, there is a problem of toughness that the material is easily destroyed by the energy applied at the time of occlusion.
• the curable composition tends to be sticky, and when the dental instrument fills the tooth cavity, the curable composition for dental restoration adheres to the instrument, which tends to deteriorate the operability. Further, there is a problem that the water resistance of the cured product of the curable composition for dental restoration is low, and the physical properties are deteriorated due to water absorption. As a factor for achieving both mechanical strength such as bending strength and toughness, the polymer structure of polycarbonate, polyarylate, or aromatic polysulfone constituting the (meth) acrylic acid ester compound (A) exhibits excellent toughness.
• the polymer structure is crosslinked so as to have a high density during polymerization, thereby increasing the mechanical strength. It is presumed that it will improve. Further, the polymer structure is also excellent in water resistance, and it is considered that the high-density crosslinked polymer obtained by polymerizing the (meth) acrylic acid ester compound (A) having the polymer structure is excellent in water resistance. Be done.
• the (meth) acrylic acid ester compound (A) does not have an extra spacer between the polymer structure and the methacryloyl group, the molecular weight can be suppressed and the viscosity can be suppressed to a low level, and the curable composition for dental restoration can be suppressed. It is presumed that it has excellent operability and can suppress the generation of bubbles in the cured product. Further, by using the (meth) acrylic acid ester compound (A), the curable composition for dental restoration is also excellent in smoothing durability.
• a known polymerizable monomer used in a curable composition for dental restoration can be used without any limitation as long as a specific mass ratio is satisfied.
• a radically polymerizable monomer is preferably used.
• the radically polymerizable monomer examples include esters such as ⁇ -cyanoacrylic acid, (meth) acrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid;
• esters such as ⁇ -cyanoacrylic acid, (meth) acrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid
• examples thereof include (meth) acrylamide-based polymerizable monomers such as (meth) acrylamide and (meth) acrylamide derivatives; vinyl esters; vinyl ethers; mono-N-vinyl derivatives; styrene derivatives and the like.
• one or more polymerizable monomers selected from the group consisting of (meth) acrylate-based polymerizable monomers and (meth) acrylamide-based polymerizable monomers are preferable, and (meth). Acrylate-based polymerizable monomers are more preferable.
• the (meth) acrylate-based polymerizable monomer is a (meth) acrylic acid ester compound (A) described later, and a (meth) acrylic acid ester compound (B) having two or more (meth) acryloyloxy groups. including.
• the notation "(meth) acrylic” is used to include both methacrylic and acrylic
• the notation “(meth) acrylate” is used to include both methacrylate and acrylate
• the notation “(meth) acryloyloxy group” is used to include both a methacryloyloxy group and an acryloyloxy group.
• the (meth) acrylic acid ester compound (A) has at least one polymer structure selected from the group consisting of polycarbonate, polyarylate, and aromatic polysulfone in one molecule, and is a repeating unit constituting the polymer structure. It is a compound in which the terminal hydroxy residue derived from is directly (meth) acryloylated. As described above, in order to obtain the effect of the present invention, a compound having the polymer structure and having a terminal hydroxy residue derived from a repeating unit constituting the polymer structure directly (meth) acryloylated. It is important to be.
• the spacer represented by "-O-A-O-" is a terminal hydroxy group in the polycarbonate. It exists between the and methacryloyl groups, the density of the polycarbonate structure is relatively low, the spacer itself is also an alkylene group, and due to its flexible skeleton, it has mechanical strength (flexural strength) as compared with the present invention. ) Is considered to decrease.
• an alkylene group and an ether bond or a urethane bond are formed between the hydroxy residues at both ends derived from the repeating unit constituting the polymer structure and the methacryloyl group. It is considered that the presence (for example, equivalent to the Polymer of Synthesis Example 6 described later) facilitates water absorption and lowers the water resistance as compared with the present invention.
• the specific structure of the polycarbonate, polyarylate, and aromatic polysulfone is not particularly limited, and examples of the polycarbonate include a polycarbonate derived from an aliphatic diol having 2 to 30 carbon atoms and an aromatic ring diol having 2 to 30 carbon atoms. Examples include polycarbonate derived from, and polycarbonate derived from a combination of these diols. Examples of the polyarylate include an amorphous polyarylate such as a polymer having an ester group derived from a diol having a bisphenol skeleton and having 12 to 30 carbon atoms and a dicarboxylic acid having 4 to 14 carbon atoms.
• aromatic polysulfone examples include a polymer derived from a diol having 2 to 30 carbon atoms and a dihalide having a sulfonyl group having 2 to 30 carbon atoms. Further, the aromatic polysulfone is represented by, for example, a polysulfone having a repeating unit represented by the following formula (1), a polyether sulfone having a repeating unit represented by the following formula (2), and a following formula (3). Examples thereof include polyphenylsulfone having a repeating unit.
• Ar represents a 2-substituted phenyl group (p-phenylene group) at the para position, and the degree of polymerization and molecular weight are not particularly limited.
• the polycarbonate structure is preferable in terms of excellent water resistance, toughness, smoothing durability and operability of the cured product.
• the (meth) acrylic acid ester compound (A) may be used alone or in combination of two or more.
• the polymer structure of the (meth) acrylic acid ester compound (A) preferably contains a cyclic structure which is a rigid skeleton in terms of excellent mechanical strength after curing.
• a cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic ring.
• Examples of the alicyclic include cyclopentane, cyclohexane, cycloheptane, dicyclodecane, tricyclodecane, adamantane, isobornyl and the like. Among these, tricyclodecane and isobornyl are more preferable.
• aromatic ring examples include benzene, naphthalene, anthracene, biphenyl, benzophenone, phenyl ether, bisphenol A and the like.
• biphenyl, benzophenone, phenyl ether and bisphenol A are more preferable.
• heterocycle examples include a heterocycle containing only a nitrogen atom as a heteroatom such as triazine, carbazole, pyrodilin, and piperidine; a heterocycle containing only an oxygen atom as a heteroatom such as tetrahydrofuran, oxane, dioxane, dioxolane, and isosorbide; Heterocycles containing oxygen and nitrogen atoms as heteroatoms such as; heterocycles containing only sulfur atoms as heteroatoms such as tetrahydrothiophene and tetrahydrothiopyran, and heterocycles containing sulfur and nitrogen atoms as heteroatoms such as thiazine and thiazole. Rings and the like can be mentioned. Among these, triazine, isosorbide, and morpholine are more preferable.
• the polymer structure of the (meth) acrylic acid ester compound (A) is independently selected from the group consisting of a carbonate group, an ester group, and a sulfonyl group because it is more excellent in toughness of the cured product. It is preferable to have three or more functional groups of the species, more preferably four or more, and even more preferably five or more.
• the polymer structure may be, for example, a structure having two or more carbonate groups and one or more sulfonyl groups, a structure having three or more carbonate groups, and three ester groups. It may have a structure having one or more, or may have a structure having three or more sulfonyl groups.
• the (meth) acrylic acid ester compound (A) contains the polymer structure, and the terminal hydroxy residue derived from the repeating unit constituting the polymer structure is directly (meth) acryloylated.
• the terminal hydroxy residue is directly (meth) acryloylized means that the oxygen atom forming the terminal hydroxy residue derived from the repeating unit constituting the polymer structure and the (meth) acryloyl group. It refers to a state in which no other atom is present between the carbon atom forming the carbonyl group.
• the reaction for directly (meth) acryloylating the terminal hydroxy residue can be carried out according to a known method, and is not particularly limited.
• the (meth) acrylic acid ester compound (A) a compound having a polymer structure that is not crosslinked in the molecule is preferable.
• the number average molecular weight (Mn) of the (meth) acrylic acid ester compound (A) is not particularly limited, but is preferably 300 to 5000, has excellent toughness of the cured product, and has a viscosity of the entire polymerizable monomer. 400 to 3500 is more preferable, and 500 to 2500 is even more preferable, from the viewpoint of keeping it low and improving the operability of the curable composition for dental restoration.
• the number average molecular weight (Mn) in the present invention means a polystyrene-equivalent number average molecular weight determined by gel permeation chromatography (GPC) and can be measured by a known method. It can be measured by the method described in the example.
• the content of the (meth) acrylic acid ester compound (A) is not particularly limited, but is preferably 1 to 40% by mass in the total amount of the polymerizable monomer, and is excellent in mechanical strength and toughness. It is more preferably to 35% by mass, further preferably 5 to 30% by mass.
• the content of the (meth) acrylic acid ester compound (A) in the curable composition for dental restoration of the present invention is not particularly limited, but is 0.1 to 20% by mass in the total amount of the curable composition for dental restoration. Is preferable, and 0.2 to 15% by mass is more preferable, and 0.5 to 10% by mass is further preferable, from the viewpoint of being more excellent in mechanical strength and toughness.
• the toughness of the obtained cured product can be further improved. .. Further, when the content of the (meth) acrylic acid ester compound (A) is 20% by mass or less in the total amount of the curable composition for dental restoration, the mechanical strength of the obtained cured product is further improved. Can be done.
• a (meth) acrylic acid ester compound (B) having two or more (meth) acryloyloxy groups in one molecule used in the present invention (hereinafter, simply referred to as "(meth) acrylic acid ester compound (B)".
• (meth) acrylic acid ester compound (B) is not particularly limited as long as it is a known (meth) acrylic acid ester compound that exhibits the effect of the present invention and is used in a curable composition for dental restoration (dental composite resin, etc.).
• the (meth) acrylic acid ester compound (A) of the present invention is excluded.
• the (meth) acrylic acid ester compound (B) having two or more (meth) acryloyloxy groups will be described.
• the (meth) acrylic acid ester compound (B) may be used alone or in combination of two or more.
• the (meth) acrylic acid ester compound (B) imparts mechanical strength to the cured product.
• (I) Bifunctional (meth) acrylic acid ester compound For example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-Hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2-bis [4- [3-acryloyloxy-2-hydroxypropoxy] phenyl] propane, 2,2 -Bis [4- [3-methacryloyloxy-2-hydroxypropoxy] phenyl] propane (Bis-GMA), 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4 -(Meta) acryloyloxypolyethoxyphenyl] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy]
• Trifunctional or higher (meth) acrylic acid ester compounds For example, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, pentaerythritol tetra (meth).
• the curable composition for dental restoration of the present invention can reduce the viscosity of the curable composition for dental restoration, impart excellent operability of a paste, and impart high mechanical strength and water resistance to the cured product.
• -2) [In the formula, R 1 and R 2 are independent groups represented by the following general formula (i) or groups represented by the general formula (ii), and X is a divalent group having 1 to 6 carbon atoms.
• R 3 and R 5 are independently divalent hydrocarbon groups having 1 to 10 carbon atoms, and R 4 and R 6 are independently hydrogen atoms or methyl groups, respectively, and k and l. Are independently integers from 0 to 6)] It can contain at least one selected from the group consisting of.
• the skeleton represented by the general formula (I) and the skeleton represented by the general formula (II) are rigid and hydrophobic. Therefore, the obtained cured product of the curable composition for dental restoration has low water absorption and can suppress a decrease in mechanical strength.
• the mono (meth) acrylic acid ester compound (E-1) and the mono (meth) acrylic acid ester compound (E-2) will be described.
• R 1 is a group represented by the general formula (i) or a group represented by the general formula (ii), and the obtained curable composition for dental restoration is excellent in curability.
• R4 and R6 are independently hydrogen atoms or methyl groups, respectively.
• R 3 and R 5 are divalent hydrocarbon groups having 1 to 10 carbon atoms independently. As the hydrocarbon group, 1 to 6 carbon atoms are preferable, and 1 to 4 carbon atoms are more preferable, because the obtained curable composition for dental restoration has good operability and excellent mechanical strength after curing. It is preferable, and 1 to 3 carbon atoms are more preferable.
• hydrocarbon group examples include a linear or branched alkylene group having 1 to 10 carbon atoms; a cycloalkylene group having 3 to 10 carbon atoms; and a phenylene group.
• k and l are independently integers of 0 to 6, and k is 0 because the viscosity of the obtained curable composition for dental restoration is low, the generation of bubbles in the cured product can be suppressed, and the curability is excellent.
• ⁇ 4 is preferable, 0 to 3 is more preferable, 0 to 2 is further preferable, and 0 or 1 is particularly preferable.
• l is preferably 0 to 4, more preferably 0 to 2, and even more preferably 0 or 1.
• Examples of the mono (meth) acrylic acid ester compound (E-1) include o-phenylphenol (meth) acrylate, m-phenylphenol (meth) acrylate, p-phenylphenol (meth) acrylate, and methoxylated-o-.
• ethoxylated-o-phenylphenol acrylate ethoxylated-m-phenylphenol acrylate, ethoxylated-o-phenylphenol acrylate, ethoxylated-o-phenylphenol acrylate, in that the paste of the obtained curable composition for dental restoration is easy to operate and has excellent mechanical strength after curing.
• Ethoxylated-p-phenylphenol acrylate, propoxylated-o-phenylphenol acrylate, propoxylated-m-phenylphenol acrylate, propoxylated-p-phenylphenol acrylate are more preferable, and ethoxylated-o-phenylphenol acrylate, ethoxylated.
• -M-Phenylphenol acrylate and ethoxylated-p-phenylphenol acrylate are more preferable, ethoxylated-o-phenylphenol acrylate and ethoxylated-m-phenylphenol acrylate are particularly preferable, and ethoxylated-o-phenylphenol acrylate is the most preferable. preferable.
• X is a divalent hydrocarbon group or an oxygen atom having 1 to 6 carbon atoms, and the obtained curable composition for dental restoration has good operability and mechanical strength after curing. Oxygen atoms are preferred because of their superiority.
• R 2 is a group represented by the above general formula (i) or a group represented by the general formula (ii), and the operability of the obtained paste of the curable composition for dental restoration is good, and after curing, it is easy to operate.
• R4 and R6 are independently hydrogen atoms or methyl groups from the viewpoint of excellent mechanical strength.
• R 3 and R 5 are divalent hydrocarbon groups having 1 to 10 carbon atoms independently.
• the hydrocarbon group 1 to 6 carbon atoms are preferable, and 1 to 4 carbon atoms are more preferable, because the obtained curable composition for dental restoration has good operability and excellent mechanical strength after curing. It is preferable, and 1 to 3 carbon atoms are more preferable.
• the hydrocarbon group include a linear or branched alkylene group having 1 to 10 carbon atoms; a cycloalkylene group having 3 to 10 carbon atoms; and a phenylene group.
• alkylene group examples include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group and an n-pentylene group.
• cycloalkylene group examples include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group and the like.
• k and l are independently integers of 0 to 6, and k is 0 to 4 because the paste of the obtained dental restoration curable composition has good operability and excellent mechanical strength after curing.
• 0 to 3 is more preferable
• 0 to 2 is further preferable
• 0 or 1 is particularly preferable.
• l is preferably 0 to 4, more preferably 0 to 2, and even more preferably 0 or 1.
• Examples of the mono (meth) acrylic acid ester compound (E-2) include o-phenoxybenzyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, p-phenoxybenzyl (meth) acrylate, and 2- (o-).
• o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, p-phenoxybenzyl acrylate in that the paste of the obtained curable composition for dental restoration is easy to operate and has excellent mechanical strength after curing
• 2- (o-Phenoxyphenyl) ethyl acrylate, 2- (m-phenoxyphenyl) ethyl acrylate, 2- (p-phenoxyphenyl) ethyl acrylate are more preferable
• o-phenoxybenzyl acrylate, m-phenoxybenzyl acrylate, p- Phenoxybenzyl acrylate is more preferable
• o-phenoxybenzyl acrylate and m-phenoxybenzyl acrylate are particularly preferable
• m-phenoxybenzyl acrylate is most preferable.
• the content of the mono (meth) acrylic acid ester compounds (E-1) and (E-2) in the curable composition for dental restoration of the present invention is 1 to 50% by mass with respect to the total amount of the polymerizable monomer. % Is preferable, and 5 to 40% by mass is more preferable, and 10 to 30% by mass is further preferable, from the viewpoint of being excellent in mechanical strength, water resistance, and operability of the paste.
• the mono (meth) acrylic acid ester compounds (E-1) and (E-2) may be used alone or in combination of two or more.
• the polymerizable monomer contained in the curable composition for dental restoration of the present invention includes (meth) acrylic acid ester compound (A) and (meth) acrylic having two or more (meth) acryloyloxy groups.
• Polymerizable monomers can also be used.
• methyl (meth) acrylate For example, methyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate.
• the polymerizable monomer contained in the curable composition for dental restoration of the present invention is substantially (meth) acrylic acid ester compound (A) and (meth) acrylic having two or more (meth) acryloyloxy groups. It may be composed of only the acid ester compound (B), the mono (meth) acrylic acid ester compound (E-1) and (E-2).
• the polymerizable monomer is a (meth) acrylic acid ester compound (A), a (meth) acrylic acid ester compound (B) having two or more (meth) acryloyloxy groups, and a mono (meth) acrylic acid.
• the composition consisting of only the ester compounds (E-1) and (E-2) means that the (meth) acrylic acid ester compound (A) is a (meth) acrylic acid ester having two or more (meth) acryloyloxy groups.
• the content of the polymerizable monomer other than the compound (B), the mono (meth) acrylic acid ester compound (E-1) and (E-2) is contained in the curable composition for dental restoration. It means that it is less than 10.0% by mass based on the total amount of the monomer, preferably less than 5.0% by mass, more preferably less than 1.0% by mass, and further preferably 0.1% by mass. It means that it is less than%, and particularly preferably less than 0.01% by mass.
• the polymerizable monomer is preferably in a liquid state, but it does not necessarily have to be in a liquid state at room temperature, and even if it is a solid polymerizable monomer, it is a polymerizable unit in another liquid state. It can also be mixed and dissolved with the body before use.
• the viscosity (25 ° C.) of each polymerizable monomer is preferably 10 Pa ⁇ s or less, more preferably 5 Pa ⁇ s or less, and even more preferably 2 Pa ⁇ s or less.
• the viscosities of the individual polymerizable monomers do not have to be within the above range and are used. In the state (mixed / diluted state), the viscosity is preferably within the above range.
• inorganic filler (C) As the inorganic filler (C) in the present invention, inorganic particles having an average primary particle diameter of 0.01 to 5 ⁇ m, which are used as a filler for dental composite resins, are used. By using such inorganic particles, the cured product is excellent in smoothing durability and mechanical strength, and the operability of the paste is excellent.
• the inorganic particles include various glasses (for example, silicon dioxide (quartz, quartz glass, silica gel, etc.), silicon as a main component and containing boron and / or aluminum together with various heavy metals), alumina, and various ceramics.
• inorganic filler (C) one type may be used alone, or two or more types may be used in combination.
• the important physical properties desired for dental materials include transparency and X-ray contrast properties similar to those of natural teeth.
• transparency can be achieved by matching the refractive indexes of the polymer of the inorganic filler (C) and the polymerizable monomer as much as possible.
• the X-ray contrast property can be imparted by using an inorganic filler (oxide or the like) containing a heavy metal element such as zirconium, barium, titanium, lanthanum, or strontium as the inorganic filler (C).
• the refractive index of such an inorganic filler containing a heavy metal element is usually high and is in the range of 1.45 to 1.65.
• the (meth) acrylic acid ester compound (A), the (meth) acrylic acid ester compound (B) and the mono (meth) acrylic acid ester compound (B) constituting the polymerizable monomer forming the polymer (meth) acrylic acid ester compound (A), (meth) acrylic acid ester compound (B) and mono (meth) acrylic acid ester compound (B)
• the refractive index of the cured product of E is usually in the range of 1.45 to 1.65, even if it is combined with such an inorganic filler having a high refractive index having X-ray contrast property, a difference in refractive index can be obtained. It can be adjusted to a small size and the transparency of the obtained dental material can be improved.
• Examples of the inorganic filler having a high refractive index capable of imparting the above-mentioned X-ray contrast property include barium borosilicate glass (for example, “E-3000” manufactured by Esstech, “8235” manufactured by Shot, and “. GM27884 “,” GM39923 “, etc.), Strontium boroaluminosilicate glass (for example,” E-4000 “manufactured by Esstech,” G018-093 “,” GM32087 “manufactured by Shot, etc.), Lantern glass (for example, Shot).
• barium borosilicate glass for example, "E-3000” manufactured by Esstech, “8235” manufactured by Shot, and “. GM27884 “,” GM39923 “, etc.
• Strontium boroaluminosilicate glass for example
• E-4000 manufactured by Esstech
• G018-093 manufactured by Shot
• GM32087 manufactured by Shot
• GM31684, etc. fluoroaluminosilicate glass (eg, Shot's "G018-091", “G018-117", etc.), zirconia-containing glass (eg, Shot's "G018-310”). , “G018-159”, etc.), glass containing strontium (eg, "G018-163", “G018-093", “GM32087”, etc. manufactured by Shot), glass containing zinc oxide (eg, Shot). (G018-161) and the like), calcium-containing glass (for example, “G018-309” and the like manufactured by Shot) and the like.
• the shape of the inorganic filler (C) is not particularly limited, and various shapes such as crushed, plate-shaped, scaly, fibrous (short fibers, long fibers, etc.), needle-shaped, whiskers, and spherical shapes are used. be able to.
• the inorganic filler (C) may be a combination of different shapes among the above shapes as long as the requirements of the present invention are satisfied.
• the average primary particle size of the inorganic filler (C) of the present invention is 0.01 to 5 ⁇ m.
• the curable composition for dental restoration is excellent in operability, and the cured product is excellent in smoothing durability and toughness.
• the average primary particle size of the inorganic filler (C) is preferably 0.02 ⁇ m or more, more preferably 0.05 ⁇ m or more, and further preferably 3 ⁇ m or less. It is more preferably 2 ⁇ m or less. If the average primary particle size is smaller than 0.01 ⁇ m, the mechanical strength is likely to be impaired, and if it is larger than 5 ⁇ m, the brittleness may increase and the toughness may decrease.
• the average primary particle size of the inorganic filler (C) can be determined by a laser diffraction / scattering method or an electron microscope observation of the particles.
• the laser diffraction / scattering method is convenient for measuring the particle size of particles having a size of 0.1 ⁇ m or more
• electron microscope observation is convenient for measuring the particle size of particles having a size of less than 0.1 ⁇ m.
• the laser diffraction / scattering method may be used to determine whether or not the thickness is 0.1 ⁇ m or more.
• a laser diffraction type particle size distribution measuring device for example, "SALD-2300" manufactured by Shimadzu Corporation
• SALD-2300 a laser diffraction type particle size distribution measuring device
• an image photograph of a particle scanning electron microscope (SEM; for example, "SU3500H-800NA type” manufactured by Hitachi High-Technologies Corporation) is taken and observed within the unit field of view of the SEM image photograph.
• the average primary particle size can be obtained by measuring the particle size of particles (200 or more) using an image analysis type particle size distribution measurement software (such as "Mac-View” manufactured by Mountech Co., Ltd.). At this time, the particle diameter of the particles is obtained as a circle-equivalent diameter which is the diameter of a circle having the same area as the area of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter.
• the content of the inorganic filler (C) in the curable composition for dental restoration of the present invention is not particularly limited, but is preferably 50 to 95% by mass, preferably 55 to 90% by mass, based on the total amount of the curable composition for dental restoration.
• the mass% is more preferable, and 60 to 85% by mass is further preferable.
• the content of the inorganic filler (C) is 50% by mass or more in the total amount of the curable composition for dental restoration, the mechanical strength of the obtained cured product can be further improved.
• the content of the inorganic filler (C) is 95% by mass or less in the total amount of the curable composition for dental restoration, the toughness of the obtained cured product can be further improved.
• the inorganic filler (C) in the present invention is preferably surface-treated with a surface-treating agent in advance.
• a surface-treating agent By using the surface-treated inorganic filler (C), the mechanical strength of the obtained curable composition for dental restoration after curing can be further improved.
• two or more kinds of inorganic fillers (C) are used, only one of them may be surface-treated, and all of them may be surface-treated. There may be. In the latter case, the inorganic fillers (C) individually surface-treated may be mixed, or a plurality of inorganic fillers may be mixed in advance and surface-treated collectively.
• a known surface treatment agent can be used, and an organic metal compound such as an organic silicon compound, an organic titanium compound, an organic zirconium compound, and an organic aluminum compound, and a phosphoric acid group, a pyrophosphate group, and a thiophosphoric acid can be used.
• An acidic group-containing organic compound having at least one acidic group such as a group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group can be used.
• the surface treatment layer may be a mixture of two or more kinds of surface treatment agents, or may be a surface treatment layer having a multi-layer structure in which a plurality of surface treatment agent layers are laminated.
• a known method can be used without particular limitation.
• Examples of the organic silicon compound include compounds represented by R 7 n SiY (4-n) (in the formula, R 7 is a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and Y is It indicates an alkoxy group, an acetoxy group, a hydroxyl group, a halogen atom or a hydrogen atom having 1 to 4 carbon atoms, and n is an integer of 0 to 3, but when there are a plurality of R7 and Y, they are the same or different. May be).
• R 7 n SiY (4-n) in the formula, R 7 is a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and Y is It indicates an alkoxy group, an acetoxy group, a hydroxyl group, a halogen atom or a hydrogen atom having 1 to 4 carbon atoms, and n is an integer of 0 to 3, but when there are a plurality of R7 and Y, they are the
• a coupling agent having a functional group capable of copolymerizing with a polymerizable monomer for example, ⁇ - (meth) acryloyloxyalkyltrimethoxysilane [(meth) acryloyloxy group and the number of carbon atoms between the silicon atom: 3-12], ⁇ - (meth) acryloyloxyalkyltriethoxysilane [carbon number between (meth) acryloyloxy group and silicon atom: 3-12], vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri Acetoxysilane, ⁇ -glycidoxypropyltrimethoxysilane and the like are preferably used.
• organic titanium compound examples include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, and tetra (2-ethylhexyl) titanate.
• organic zirconium compound examples include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, and zirconium acetate.
• organoaluminum compound examples include aluminum acetylacetonate and aluminum organolate chelate compounds.
• Examples of the acidic group-containing organic compound having a phosphate group include 2-ethylhexyl acid phosphate, stearyl acid phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, and the like.
• the acidic group-containing organic compound having an acidic group such as a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group and a carboxylic acid group
• those described in International Publication No. 2012/042911 are preferable. Can be used for.
• the above surface treatment agent may be used alone or in combination of two or more. Further, an acidic group having a functional group capable of copolymerizing with the polymerizable monomer in order to enhance the chemical bondability between the inorganic filler (C) and the polymerizable monomer and improve the mechanical strength of the cured product. It is more preferable to use the contained organic compound.
• the amount of the surface treatment agent used is not particularly limited, and for example, 0.1 to 50 parts by mass is preferable with respect to 100 parts by mass of the inorganic filler (C).
• polymerization initiator (D) of the present invention will be described.
• the polymerization initiator (D) include a heat polymerization initiator, a photopolymerization initiator, and a chemical polymerization initiator. These may be used alone or in combination of two or more.
• heat polymerization initiator examples include organic peroxides and azo compounds.
• organic peroxide examples include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates and the like.
• ketone peroxide examples include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide and the like.
• hydroperoxide examples include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzenehydroperoxide, cumene hydroperoxide, t-butylhydroperoxide and 1,1,3,3-tetramethylbutylhydroperoxide. Can be mentioned.
• diacyl peroxide examples include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide.
• dialkyl peroxide examples include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 1,3-bis (t).
• dialkyl peroxide examples include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 1,3-bis (t).
• -Butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexane and the like can be mentioned.
• peroxyketal examples include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and 2,2-bis (t-butylperoxy).
• peroxy ester examples include ⁇ -cumyl peroxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, and t.
• peroxydicarbonate examples include di-3-methoxyperoxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, and di-n-propylperoxy. Examples thereof include dicarbonate, di (2-ethoxyethyl) peroxydicarbonate and diallylperoxydicarbonate.
• diacyl peroxide is preferable, and benzoyl peroxide is more preferable, from the viewpoint of overall balance of safety, storage stability and radical generation ability.
• Examples of the azo compound include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), and the like. Examples thereof include 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis (isobutyrate), and 2,2'-azobis (2-amidinopropane) dihydrochloride.
• photopolymerization initiator examples include (bis) acylphosphine oxides, ⁇ -diketones, coumarins and the like.
• examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide.
• 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi (2,6-dimethylphenyl) Phosphate, salts thereof and the like can be mentioned.
• bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6-dichlorobenzoyl)-.
• ⁇ -diketones examples include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, acenaphthenicinone and the like. Be done. Of these, camphorquinone is preferable.
• Examples of the coumarins include 3,3'-carbonylbis (7-diethylaminocoumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienoyl coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl.
• At least one selected from the group consisting of (bis) acylphosphine oxides, ⁇ -diketones, and coumarins widely used in dental curable compositions should be used. Is preferable.
• Such a photopolymerization initiator may be further combined with a polymerization accelerator, if necessary, to enable photopolymerization efficiently in a shorter time.
• polymerization accelerator suitable for the photopolymerization initiator examples include tertiary amines, aldehydes, compounds having a thiol group, sulfinic acid and / or salts thereof.
• tertiary amine examples include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-.
• aldehydes include dimethylaminobenzaldehyde and terephthalaldehyde.
• Examples of the compound having a thiol group include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, thiobenzoic acid and the like.
• sulphonic acid and salts thereof include benzenesulphonic acid, sodium benzenesulphonate, potassium benzenesulphonate, calcium benzenesulfinate, lithium benzenesulphonate, p-toluenesulfate, sodium p-toluenesulfate, and p-toluene.
• Potassium sulphinate calcium p-toluene sulphinate, lithium p-toluene sulphinate, 2,4,6-trimethylbenzene sulphonic acid, sodium 2,4,6-trimethylbenzene sulphinate, 2,4,6-trimethylbenzene sulphine Potassium Acid, Calcium 2,4,6-trimethylbenzeneSulfinate, Lithium 2,4,6-trimethylbenzeneSulfinate, 2,4,6-Triethylbenzenesulfinate, Sodium 2,4,6-Triethylbenzenesulfinate, Potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, 2, , 4,6-Triisopropylbenzene Potassium sulphinate, 2,4,6-tri
• a redox-based polymerization initiator such as an organic peroxide and an amine-based; organic peroxide, an amine and a sulfinic acid (or a salt thereof) -based is preferably used.
• a redox-based polymerization initiator it is necessary to take a packaging form in which the oxidizing agent and the reducing agent are separately packaged, and mix the two immediately before use.
• the oxidizing agent of the redox-based polymerization initiator include organic peroxides.
• the organic peroxide is not particularly limited as the oxidizing agent of the redox-based polymerization initiator, and known ones can be used. Specific examples thereof include organic peroxides exemplified by the heat polymerization initiator.
• diacyl peroxide is preferably used from the viewpoint of overall balance of safety, storage stability and radical generation ability, and among them, benzoyl peroxide is more preferably used.
• an aromatic tertiary amine having no electron-withdrawing group in the aromatic ring is usually used.
• the aromatic tertiary amine having no electron-withdrawing group in the aromatic ring 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
• the chemical polymerization initiator may be used in combination with a polymerization accelerator, if necessary.
• the polymerization accelerator of the chemical polymerization initiator can be selected from the polymerization accelerators used in the general industry, and among them, the polymerization accelerator used for dental applications is preferably used.
• the polymerization accelerator may be used alone or in combination of two or more. Specific examples thereof include amines, sulfinic acid and salts thereof, copper compounds, tin compounds and the like.
• the amines used as the polymerization accelerator of the chemical polymerization initiator are classified into aliphatic amines and aromatic amines having an electron-withdrawing group in the aromatic ring.
• the aliphatic amine include aliphatic primary amines such as n-butylamine, n-hexylamine and n-octylamine; and aliphatic secondary amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethylmethacrylate, N-methyldiethanolaminedimethacrylate, N-ethyldiethanolaminedimethacrylate, triethanolamine monomethacrylate , Triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, tri
• Examples of the aromatic tertiary amine having an electron-withdrawing group in the aromatic ring used as the polymerization accelerator of the chemical polymerization initiator include ethyl 4- (N, N-dimethylamino) benzoate, 4- ( Methyl N, N-dimethylamino) benzoate, 4- (N, N-dimethylamino) n-butoxyethyl benzoate, 4-N, N-dimethylamino benzoate 2- (methacryloyloxy) ethyl, 4- (N) , N-dimethylamino) benzophenone, 4- (N, N-dimethylamino) butyl benzoate and the like.
• Examples of the sulfinic acid and its salt used as the polymerization accelerator include those exemplified as the polymerization accelerator of the above-mentioned photopolymerization initiator, sodium benzenesulfinate, sodium p-toluenesulfinate, 2,4,6-. Sodium triisopropylbenzenesulfinate is preferred.
• the copper compound used as the polymerization accelerator for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.
• tin compound used as the polymerization accelerator examples include di-n-butyl tin dimaleate, di-n-octyl tin dimaleate, di-n-octyl tin dilaurate, and di-n-butyl tin dilaurate.
• Particularly suitable tin compounds are di-n-octyl tin dilaurate and di-n-butyl tin dilaurate.
• a photopolymerization initiator because of the convenience of curing in the oral cavity, while for dental mill blanks, the degree of polymerization is increased. It is preferable to use a heat polymerization initiator because it improves the strength.
• the content of the polymerization initiator (D) in the present invention is not particularly limited, but is 0.001 to 30 parts by mass with respect to 100 parts by mass of the polymerizable monomer from the viewpoint of curability and the like of the obtained composition. Is preferable.
• the content of the polymerization initiator (D) is 0.001 part by mass or more with respect to 100 parts by mass of the polymerizable monomer, there is no possibility that the polymerization will proceed sufficiently and the mechanical strength will be lowered. It is preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more.
• the content of the polymerization initiator (D) is 30 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, sufficient mechanical strength is sufficient even when the polymerization performance of the polymerization initiator itself is low. Further, there is no possibility of causing precipitation from the composition, and more preferably, it is 20 parts by mass or less.
• the curable composition for dental restoration of the present invention includes a pH adjuster, an ultraviolet absorber, an antioxidant, a colorant (pigment, dye), an antibacterial agent, and an X-ray contrast agent, depending on the purpose.
• a thickener, a fluorescent agent, a cross-linking agent (a metal ion-releasing component such as a polyvalent metal ion-releasing filler, etc.) and the like can be further added.
• the crosslink density becomes too high, the brittleness increases, so that the increase in the crosslink density is suppressed. Examples include sex compositions.
• the pigment may be any of an inorganic pigment and / or an organic pigment, and the inorganic pigment may be, for example, a sulfide such as chlorophyll, zinc yellow, barium yellow; a ferrocyanide such as navy blue; silver vermilion, cadmium yellow, etc.
• Sulfides such as zinc sulfide and cadmium red; sulfates such as barium sulfate, zinc sulfate and strontium sulfate; oxides such as antimony white, zinc flower, titanium white, red iron oxide and chromium oxide; water such as aluminum hydroxide Oxides; silicates such as calcium silicate and ultramarine; carbons such as carbon black and graphite may be mentioned.
• the organic pigment include ditron pigments such as Naftor Green B and Naftor Green Y; nitro pigments such as Naftor Yellow S and Resole Fast Yellow 2G; Permanent Red 4R, Brilliant Fast Scarlet, Hansa Yellow, Benzidine Yellow and the like.
• Insoluble azo pigments Insoluble azo pigments; sparingly soluble azo pigments such as resole red, lake red C, lake red D; soluble azo pigments such as Brilliant Carmine 6B, Permanent Red F5R, Pigment Scarlet 3B, Bordeaux 10B; Phtalocyanin pigments such as Sky Blue; basic dye pigments such as Rhodamine Lake, Malakite Green Lake, and Methyl Violet Lake; acidic dye pigments such as Peacock Blue Lake, Eosin Lake, and Kinolin Yellow Lake.
• the pigment may be used alone or in combination of two or more, and may be appropriately selected according to the desired color tone.
• the content of the pigment in the curable composition for dental restoration is appropriately adjusted according to a desired color tone and is not particularly limited, but is preferably 0.000001 parts by mass with respect to 100 parts by mass of the curable composition for dental restoration.
• the above is more preferably 0.00001 parts by mass or more, preferably 5 parts by mass or less, and more preferably 1 part by mass or less.
• the method for producing the curable composition for dental restoration of the present invention includes, for example, the following steps (1) and (2).
• Kneading step is a step of performing a kneading operation, and a polymerizable single amount of the (meth) acrylic acid ester compound (A) and the (meth) acrylic acid ester compound (B) in the kneader container.
• the body and the polymerization initiator (D) are added to prepare a polymerizable monomer-containing composition
• the inorganic filler (C) is further added and kneaded to prepare a paste-like composition.
• the kneading method is not particularly limited as long as the effect of the present invention is exhibited, and a known method can be adopted. However, from the viewpoint of shortening the kneading time and preventing the occurrence of paste variation, heating is performed. It is preferable to knead while kneading.
• the kneading temperature is preferably 40 to 60 ° C. If the temperature is lower than 40 ° C, the effect of shortening the kneading time cannot be sufficiently obtained, and if the temperature exceeds 60 ° C, polymerization curing or deterioration of the composition may occur during kneading. Further, during kneading, vacuum defoaming treatment can be performed if necessary. At this time, the degree of vacuum is not particularly limited, but the degree of vacuum is preferably 5 to 200 Torr in order to efficiently remove air bubbles.
• the defoaming step is a step of performing defoaming work. After putting the paste-like composition into the defoaming machine container, pressure is applied while removing air bubbles inside the paste by reducing the pressure. While extruding out of the container, defoaming is performed.
• the defoaming conditions are not particularly limited, but in order to efficiently remove air bubbles, polymerizable monomers such as the (meth) acrylic acid ester compound (A) and the (meth) acrylic acid ester compound (B), and the polymerization initiator.
• the degree of vacuum is preferably 5 to 200 Torr in order to prevent the composition containing the polymerizable monomer containing (D) from separating from the inorganic filler (C).
• the depressurization time is preferably 3 to 30 minutes. Further, the pressure at the time of extrusion is preferably 0.5 to 5 MPa. The pressurization time is preferably 3 to 30 minutes. In addition, heat treatment can be performed as needed during defoaming. At this time, the temperature is not particularly limited, but the temperature is preferably 40 to 60 ° C. in order to efficiently remove bubbles.
• the curable composition for dental restoration of the present invention has high mechanical strength and toughness, is excellent in water resistance and slipping durability, and is excellent in operability of the curable composition for dental restoration. Since it can suppress bubbles generated in the cured product and has an excellent appearance, it can be suitably used as a dental material. Specifically, in the field of dentistry, it can be suitably used as a dental material (particularly a dental composite resin) that can replace a part or the whole of a natural tooth. Therefore, an embodiment of the present invention includes a dental composite resin made of a curable composition for dental restoration.
• the cured product obtained by polymerizing and curing the curable composition for dental restoration of the present invention is used as a dental mill blank, which is a material to be cut used in a CAD / CAM system produced by cutting with a milling device. It can be suitably used. Therefore, another embodiment of the present invention includes a dental mill blank made of a cured product of a curable composition for dental restoration.
• EPPA Ethoxylation-o-phenylphenol acrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
• the organic layer was washed in the order of distilled water, 1M aqueous hydrochloric acid solution, and saturated aqueous sodium carbonate solution, and dried over magnesium sulfate. After concentrating the dried solution, it is poured into methanol, the precipitate is collected by filtration, and vacuum-dried, so that the hydroxy residues at both ends derived from the repeating units constituting the polymer structure are directly methacryloylated.
• PCIS-3 number average molecular weight: 936
• the organic layer was washed in the order of distilled water, 1M aqueous hydrochloric acid solution, and saturated aqueous sodium carbonate solution, and dried over magnesium sulfate. After concentrating the dried solution, it is poured into methanol, the precipitate is collected by filtration, and vacuum dried to directly methacrylic acidize the hydroxy residues at both ends derived from the repeating units constituting the polymer structure.
• PARM number average molecular weight: 1036
• PCUMA number average molecular weight: 1200
• PCUMA number average molecular weight: 1200
• the number average molecular weight (Mn) of the (meth) acrylic acid ester compound (A) was measured by gel permeation chromatography (GPC) as follows. First, at room temperature, the compounds synthesized in each of the above-mentioned Synthesis Examples 1 to 6 were dissolved in tetrahydrofuran (containing THF and 0.5 mg / mL BHT) so as to be 0.5 mg / mL each. Then, the obtained solution was filtered through a solvent-resistant membrane filter "Mysholidisc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 ⁇ m to obtain a sample solution.
• Mysholidisc manufactured by Tosoh Corporation
• the sample solution was adjusted so that the concentration of the component soluble in THF was 0.8% by mass. This sample solution was used for measurement under the following conditions.
• Equipment High-speed GPC equipment "HLC-8220GPC” [manufactured by Tosoh Corporation] Column: LF-604 2 series [manufactured by Showa Denko KK] Eluent: THF Flow rate: 0.6 mL / min Oven temperature: 40 ° C
• Sample injection volume 0.020 mL
• standard polystyrene resin for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) so that each becomes 0.5 mg / mL.
• the elution peak of the sample may overlap with the ghost derived from the solvent and become unclear (under the above conditions, the molecular weight is approximately 400 g / mol or less), but the components having the molecular weight or less are excluded from the calculation. It was decided to obtain the average molecular weight.
• a polymerizable monomer-containing composition (M10) was prepared by dissolving 0.5 parts by mass of THP as a heat polymerization initiator in 80 parts by mass of D2.6E and 20 parts by mass of PCIS-3.
• a polymerizable monomer-containing composition (M14) was prepared by dissolving 1.5 parts by mass of BPO as a heat polymerization initiator in 70 parts by mass of UDMA and 30 parts by mass of TEGDMA.
• composition of each polymerizable monomer-containing composition is shown in Table 1 below.
• composition of the filler (F1 to F5) is shown in Table 2 below.
• the curable composition for dental restoration of each of the manufactured Examples and Comparative Examples is vacuum defoamed, filled in a stainless steel mold (dimensions: 2 mm ⁇ 2 mm ⁇ 25 mm), and slid up and down. It was pressure-welded with glass and cured by irradiating both sides with light using a dental visible light irradiator (Pencure 2000, manufactured by Morita Co., Ltd.) for 10 seconds per point, 5 points on each side. For each Example and Comparative Example, 5 cured products were prepared as samples.
• the measurement was carried out in the same manner as the above-mentioned measurement of the dental composite resin sample, except that the points and the points where 10 cured products were prepared as samples.
• the bending strength of the dental composite resin is judged to be good at 150 MPa or more, and further better at 180 MPa or more. Further, the fracture energy of the dental composite resin is judged to be good at 13 mJ or more, and further better at 15 mJ or more.
• the bending strength as a dental mill blank is judged to be good at 200 MPa or more, and further good at 240 MPa or more. Further, the fracture energy of the dental mill blank is judged to be good when it is 30 mJ or more, and further good when it is 32 mJ or more. From the viewpoint of mechanical strength and toughness, it is preferable that both the bending strength and the breaking energy satisfy the above range.
• the curable compositions for dental restoration of each of the manufactured Examples and Comparative Examples are vacuum defoamed and then filled in a stainless steel mold (dimensions: 1.5 mm ⁇ 15 mm ⁇ 15 mm), and the upper and lower parts are placed.
• a stainless steel mold dimensions: 1.5 mm ⁇ 15 mm ⁇ 15 mm
• the upper and lower parts are placed.
• ⁇ -light V LED polymerizer for dental technology
• a test piece 1.5 mm ⁇ 15 mm ⁇ 15 mm
• the obtained cured product and its test piece were polished in the order of # 1000 abrasive paper, # 2000 abrasive paper, and # 3000 abrasive paper under dry conditions, and finally polished with a lapping film.
• toothbrush wear test teethbrush: "Biteen Lion” (hardness: normal; manufactured by Lion Corporation)
• toothpaste "Denter Clear MAX” (manufactured by Lion Corporation)
• load 250 g
• the glossiness retention rate (%) was calculated by dividing the glossiness after the obtained toothbrush wear test by the glossiness before the test, and the glossiness durability was evaluated.
• the glossiness retention rate is preferably 85% or more, more preferably 90% or more, and further preferably 93% or more.
• the average value was calculated and used as an evaluation of the operability of the paste.
• the adhesive force is preferably 1.5 N or less, more preferably 1.0 N or less.
• the adhesive force is 2.0 N or more, it is judged that the operability of the paste when filling with a dental instrument is low.
• the number of the cured product having bubbles is preferably 1 or less, and more preferably 0. On the other hand, if the number is three or more, it is judged that the quality is poor from the viewpoint of deterioration of mechanical strength and deterioration of appearance.
• Examples 1 to 12, Comparative Examples 1 to 3 (dental composite resin) Using the polymerizable monomer-containing compositions (M1-9, M11, M12) obtained in the above production example and the fillers (F1 to F4), the mixture was mixed and kneaded at the composition ratio shown in Table 3 below. The uniform was vacuum defoamed to prepare paste-like curable compositions for dental restoration of Examples 1 to 12 and Comparative Examples 1 to 3. The prepared curable composition for dental restoration was tested. The results are shown in Table 3 below.
• the operability of the pastes obtained in Examples 1 to 12 was all good. Further, it was found that the cured product had high bending strength and breaking energy, and was excellent in water resistance without a decrease in strength due to immersion in water at 37 ° C. assuming the oral cavity. Furthermore, it was found that the cured product did not lose its glossiness even when the toothbrush or the like was worn, and was excellent in smoothness durability. On the other hand, the cured product obtained in Comparative Example 1 had a not bad initial fracture energy, but had a significantly low water resistance.
• Comparative Example 1 an alkylene group and a urethane bond are present between the hydroxy residues at both ends derived from the repeating unit in which PCUMA included in the compound disclosed in Patent Document 1 constitutes a polymer structure and the methacryloyl group. It is considered that the density of the polymer structure is relatively low due to the structure of the polymer structure, and the presence of urethane bonds absorbs water and the water resistance is lowered. Further, the cured product obtained in Comparative Example 2 had low water resistance and very low fracture energy. Further, the cured product obtained in Comparative Example 3 had low mechanical strength, and the operability of the paste and the smoothing durability of the cured product were very poor.
• Examples 13 to 15, Comparative Examples 4 and 5 (Dental mill blank) Using the polymerizable monomers (M10, M13, M14) obtained in the above production example and the fillers (F1 to F3, F5), they are mixed and kneaded uniformly at the composition ratio shown in Table 4 below. Was vacuum defoamed to prepare paste-like curable compositions for dental restoration of Examples 13 to 15 and Comparative Examples 4 and 5. Then, the curable composition for dental restoration was poured into a 20 mm ⁇ 30 mm ⁇ 60 mm rectangular mold and heated at 50 ° C. for 1 hour. Then, while pressurizing at 1 MPa, heat treatment was performed at 150 ° C. for 1 hour to obtain a cured product as a dental mill blank. The obtained cured product was tested. The results are shown in Table 4 below.
• the curable composition for dental restoration of the present invention has excellent paste operability, the cured product has high mechanical strength and toughness, and is excellent in water resistance and slipping durability.
• the curable composition for dental restoration of the present invention has excellent paste operability, the cured product has high mechanical strength and toughness, and is excellent in water resistance and slipping durability. That is, it is easy to handle, has sufficient mechanical strength to replace natural teeth, and is suitably used as a material for repairing tooth defects and caries, especially as a dental composite resin. Further, the cured product is suitably used as a dental mill blank.

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• 2021
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