Dental polymerizable composition, resin material for dental cutting, and method for producing same

Abstract

Provided is a dental polymerizable composition comprising a first polymerizable monomer, a second polymerizable monomer, and an inorganic filler, the composition being characterized in that: the first polymerizable monomer has only one group selected from the group consisting of a urethane group, a urea group, and a carbonate group; and the second polymerizable monomer includes a structure represented by general formula (1) or a structure represented by general formula (2). (In general formula (1), Y1 is an aromatic hydrocarbon group which may contain a heteroatom, R11 and R12 are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, X11 and X12 may be different from each other in the same repeating unit, and are a hydrogen atom or an alkyl group having 5 or less carbon atoms, a is an integer of 1-4, b is a number of 1-30, c is an integer of 1-4, d is a number of 1-30, and the sum of b and d is a number of 2-31) (In general formula (2), Z1 and Z2 are each independently any one selected from the group consisting of a urethane group, a urea group, and a carbonate group, Y2 is a chain hydrocarbon group which has 30 or less carbon atoms and may contain a hetero atom, an alicyclic hydrocarbon group which has 30 or less carbon atoms and may contain a hetero atom, or an aromatic hydrocarbon group which has 30 or less carbon atoms and may contain a hetero atom, and R21 and R22 are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, X21 and X22 may be different from each other in the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms, e is an integer of 1-4, f is a number of 1-10, g is an integer of 1-4, h is a number of 1-10, and the sum of f and h is a number of 2-11.)

Description

Dental polymerizable composition, dental cutting resin material and method for producing the same

[0001] The present invention relates to a dental polymerizable composition, a resin material for dental cutting, and a method for producing the same.

[0002] In recent years, CAD / CAM systems have been used to design crowns, bridges, and other dental prostheses on a computer screen and then manufacture them by cutting. These CAD / CAM systems can provide dental prostheses of consistent quality in a short period of time.

[0003] In the cutting process of dental prostheses, a dental resin material for cutting processing, which is formed into a block of dental resin, is used as the material before being cut into a shape (see, for example, Patent Document 1).

[0004] Patent No. 6739809

[0005] The resin material for dental cutting described in Patent Document 1 has the problem of deterioration due to absorption of moisture in the oral cavity. Furthermore, a resin material for dental cutting used to manufacture dental prostheses is desired to have excellent mechanical strength to ensure stability in the oral cavity.

[0006] Therefore, an object of the present invention is to provide a dental polymerizable composition capable of forming a resin material for dental cutting work, which has excellent mechanical strength and low water absorption.

[0007] The dental polymerizable composition of the present invention as a means for solving the problems is a dental polymerizable composition comprising a first polymerizable monomer, a second polymerizable monomer, and an inorganic filler, wherein the first polymerizable monomer has only one group selected from the group consisting of a urethane group, a urea group, and a carbonate group, and the second polymerizable monomer has a structure represented by the following general formula (1) or a structure represented by the following general formula (2):

[0008] (In general formula (1), Y １ is an aromatic hydrocarbon group which may contain a heteroatom, and R １１ and R １２are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X １１ and X １２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; a is an integer of 1 to 4; b is a number of 1 to 30; c is an integer of 1 to 4; d is a number of 1 to 30; and the sum of b and d is a number of 2 to 31.

[0009] (In general formula (2), Z １ and Z ２ are each independently any one selected from the group consisting of a urethane group, a urea group, and a carbonate group; Y ２ is a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, and R ２１ and R ２２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ２１ and X ２２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; e is an integer of 1 to 4; f is a number of 1 to 10; g is an integer of 1 to 4; h is a number of 1 to 10; and the sum of f and h is a number of 2 to 11.

[0010] According to the present invention, it is possible to provide a dental polymerizable composition capable of forming a dental cutting resin material having excellent mechanical strength and low water absorption.

[0011] The present invention will be described in detail below.

[0012] (Dental polymerizable composition) The dental polymerizable composition of the present invention contains a first polymerizable monomer, a second polymerizable monomer, and an inorganic filler, and may contain other polymerizable monomers and other components as necessary.

[0013] <First Polymerizable Monomer> The first polymerizable monomer in the present invention has only one group (hereinafter, may be referred to as a urethane group, etc.) selected from the group consisting of a urethane group, a urea group, and a carbonate group, and may have other groups as necessary.

[0014] The first polymerizable monomer having only one urethane group or the like has only one urethane group or the like, and does not have two or more urethane groups or the like.

[0015] The first polymerizable monomer imparts mechanical strength to a cured product obtained by curing the dental polymerizable composition.

[0016] The urethane group is a linking group represented by -NHCOO-, the urea group is a linking group represented by -NHCONH-, and the carbonate group is a linking group represented by -OCOO-.

[0017] The first polymerizable monomer is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include (meth)acrylates having only one urethane group or the like.

[0018] In this specification, (meth)acrylate refers to a compound having a methacryloyloxy group and / or an acryloyloxy group (hereinafter referred to as a (meth)acryloyloxy group).

[0019] The (meth)acrylate having only one urethane group or the like is not particularly limited and can be appropriately selected depending on the purpose, but a (meth)acrylate having two or more (meth)acryloyloxy groups is preferred.

[0020] The (meth)acrylate having only one urethane group or the like is not particularly limited and can be appropriately selected depending on the purpose, but is preferably represented by the following formula (1).

[0021] (In formula (1), A １ and A ２ are each independently a (meth)acryloyloxy group or a (meth)acrylamide group which may have an alkyl group having 3 or less carbon atoms on the side chain, B is a urethane group, and R １ and R ２are each independently an alkyl group having 8 or less carbon atoms which may have a (meth)acryloyloxy group or a (meth)acrylamide group on the side chain.

[0022] In this specification, the term "(meth)acrylamide group" refers to a methacrylamide group and / or an acrylamide group. The acrylamide group is defined as -NHCO(CH=CH ２ ) represents a substituent represented by the formula:

[0023] In the formula (1), A １ and A ２ Preferably, the number of carbon atoms in the alkyl group on the side chain of the (meth)acryloyloxy group or (meth)acrylamide group is 2 or less, and more preferably, the side chain of the (meth)acryloyloxy group or (meth)acrylamide group does not have an alkyl group.

[0024] In the formula (1), R １ and R ２ The alkyl group preferably has 5 or less carbon atoms.

[0025] R １ and R ２ When the alkyl group has 8 or less carbon atoms, distortion of the polymerizable monomer having only one urethane group or the like is suppressed, and the cured product obtained by curing the dental polymerizable composition has sufficient mechanical strength.

[0026] Specific examples of the (meth)acrylate containing only one urethane group or the like represented by the formula (1) include (meth)acrylates represented by the following formulas (2) to (6).

[0027] The (meth)acrylate represented by the formula (2) is sometimes called mUDMA.

[0028]

[0029]

[0030]

[0031]

[0032] The content of the first polymerizable monomer is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of imparting high mechanical strength to a cured product of the dental polymerizable composition, the content of the first polymerizable monomer is preferably 5% by mass or more and 50% by mass or less with respect to the total amount of the dental polymerizable composition.

[0033] The analytical method for confirming whether or not the dental polymerizable composition contains the first polymerizable monomer is not particularly limited and can be appropriately selected depending on the purpose. For example, nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), Raman spectroscopy, mass spectroscopy (MS), etc. can be used to confirm whether or not the dental polymerizable composition contains the first polymerizable monomer.

[0034] As the first polymerizable monomer, a suitably synthesized product or a commercially available product may be used.

[0035] <Second Polymerizable Monomer> The second polymerizable monomer in the present invention contains a structure represented by the following general formula (1) or a structure represented by the following general formula (2), and may contain other structures as necessary.

[0036] The second polymerizable monomer imparts low water absorbency to the cured product obtained by curing the dental polymerizable composition.

[0037] (In general formula (1), Y １ is an aromatic hydrocarbon group which may contain a heteroatom, and R １１ and R １２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X １１ and X １２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; a is an integer of 1 to 4; b is a number of 1 to 30; c is an integer of 1 to 4; d is a number of 1 to 30; and the sum of b and d is a number of 2 to 31.

[0038] (In general formula (2), Z １ and Z ２ are each independently any one selected from the group consisting of a urethane group, a urea group, and a carbonate group; Y ２is a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, and R ２１ and R ２２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ２１ and X ２２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; e is an integer of 1 to 4; f is a number of 1 to 10; g is an integer of 1 to 4; h is a number of 1 to 10; and the sum of f and h is a number of 2 to 11.

[0039] <<Structure Represented by General Formula (1)>>

[0040] (In general formula (1), Y １ is an aromatic hydrocarbon group which may contain a heteroatom, and R １１ and R １２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X １１ and X １２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; a is an integer of 1 to 4; b is a number of 1 to 30; c is an integer of 1 to 4; d is a number of 1 to 30; and the sum of b and d is a number of 2 to 31.

[0041] In the general formula (1), X １１ and X １２ is preferably a hydrogen atom or a methyl group.

[0042] In the general formula (1), R １１ and R １２ is preferably a hydrogen atom or a methyl group.

[0043] In the general formula (1), a is preferably an integer of 1 to 3.

[0044] In the general formula (1), b is preferably a number from 1 to 15.

[0045] In the general formula (1), c is preferably an integer of 1 to 3.

[0046] In the general formula (1), d is preferably a number from 1 to 15.

[0047] In the general formula (1), b and d each represent an average value, and the sum of b and d is preferably a number from 2 to 18.

[0048] The aromatic hydrocarbon group in the general formula (1) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably any of the structures represented by the following general formula (1-1).

[0049] (In general formula (1-1), R ２３ , R ２４ , R ２５ , R ２６ , R ２７ , and R ２８ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may contain a heteroatom, and are preferably a hydrogen atom or a methyl group. Among these, a structure represented by the following general formula (1-2) is preferred:

[0050] (In general formula (1-2), R ２３ , R ２４ , R ２５ , R ２６ , R ２７ , and R ２８ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may contain a heteroatom, and are preferably a hydrogen atom or a methyl group.

[0051] <<Structure Represented by General Formula (2)>>

[0052] (In general formula (2), Z １ and Z ２ are each independently any one selected from the group consisting of a urethane group, a urea group, and a carbonate group; Y ２is a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, and R ２１ and R ２２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ２１ and X ２２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; e is an integer of 1 to 4; f is a number of 1 to 10; g is an integer of 1 to 4; h is a number of 1 to 10; and the sum of f and h is a number of 2 to 11.

[0053] In the general formula (2), X ２１ and X ２２ is preferably a hydrogen atom or a methyl group.

[0054] In the general formula (2), R ２１ and R ２２ is preferably a hydrogen atom or a methyl group.

[0055] In the general formula (2), e is preferably an integer of 1 to 3.

[0056] In the general formula (2), f is preferably a number of 1 to 6.

[0057] In the general formula (2), g is preferably an integer of 1 to 3.

[0058] In the general formula (2), h is preferably a number of 1 to 6.

[0059] In the general formula (2), f and h each represent an average value, and the sum of f and h is preferably a number from 2 to 6.

[0060] The alicyclic hydrocarbon group and aromatic hydrocarbon group in the general formula (2) are not particularly limited and can be appropriately selected depending on the purpose, but are preferably any of the structures represented by the following general formula (2-1):

[0061] (In general formula (2-1), R ３３ , R３４ , R ３５ , R ３６ , R ３７ , R ３８ , and R ３９ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may contain a heteroatom, and are preferably a hydrogen atom or a methyl group.

[0062] From the viewpoint of excellent hydrophobicity, the second polymerizable monomer preferably contains at least one selected from the structure represented by the following general formula (3) and the structure represented by the following general formula (4):

[0063] (In general formula (3), R ３１ and R ３２ is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ３１ and X ３２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; i is an integer of 1 to 3; j is a number of 1 to 9; k is an integer of 1 to 3; l is a number of 1 to 9; and the sum of j and l is a number of 2 to 10.

[0064] (In general formula (4), R ４１ and R ４２ is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ４１ and X ４２ may be different from one another within the same repeating unit, and each represents a hydrogen atom or an alkyl group having 5 or less carbon atoms; Y ４ represents a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, m is an integer of 1 to 3, n is a number of 1 to 5, o is an integer of 1 to 3, p is a number of 1 to 5, and the sum of n and p is a number of 2 to 8).

[0065] <<Structure Represented by General Formula (3)>>

[0066] (In general formula (3), R ３１ and R３２ is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ３１ and X ３２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; i is an integer of 1 to 3; j is a number of 1 to 9; k is an integer of 1 to 3; l is a number of 1 to 9; and the sum of j and l is a number of 2 to 10.

[0067] In the general formula (3), the numbers j and l are each an average value.

[0068] Specific examples of the polymerizable monomer having a structure represented by general formula (3) include 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 2.3), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 2.6, commonly known as D-2.6E), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 4), and 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 10).

[0069] The average number of moles of ethyleneoxy groups added in the polymerizable monomer containing the structure represented by formula (3) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 2 or more and 9 or less.

[0070] <<Structure Represented by General Formula (4)>>

[0071] (In general formula (4), R ４１ and R ４２ is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ４１ and X ４２ may be different from one another within the same repeating unit, and each represents a hydrogen atom or an alkyl group having 5 or less carbon atoms; Y ４represents a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, m is an integer of 1 to 3, n is a number of 1 to 5, o is an integer of 1 to 3, p is a number of 1 to 5, and the sum of n and p is a number of 2 to 8).

[0072] In the general formula (4), the numbers n and p are each an average value.

[0073] Specific examples of polymerizable monomers containing the structure represented by general formula (4) include di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate (UDMA).

[0074] The content of the second polymerizable monomer is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of imparting excellent low water absorption to the cured product of the dental polymerizable composition, it is preferably 0.5% by mass or more and 30% by mass or less relative to the total amount of the dental polymerizable composition.

[0075] The analytical method for confirming whether or not the dental polymerizable composition contains the second polymerizable monomer is not particularly limited and can be appropriately selected depending on the purpose. For example, confirmation can be made by nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), Raman spectroscopy, and mass spectrometry (MS).

[0076] As the second polymerizable monomer, a suitably synthesized product or a commercially available product may be used.

[0077] <Other Polymerizable Monomers> The other polymerizable monomers are not particularly limited and can be appropriately selected as long as the effects of the present invention are not impaired. Examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerol di(meth)acrylate, bisphenol A diglycidyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0078] The content of the other polymerizable monomers is not particularly limited and can be appropriately selected within a range that does not impair the effects of the present invention.

[0079] As the other polymerizable monomers, those synthesized appropriately or commercially available products may be used.

[0080] <Inorganic filler>

[0081] The inorganic filler is preferably made of an inorganic material, and is preferably contained in the dental polymerizable composition in the form of particles.

[0082] The inorganic filler is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include barium glass, strontium glass, fluoroaluminosilicate glass, and silica fine powder.

[0083] The inorganic filler is preferably hydrophobized, for example, by using a silane coupling agent.

[0084] The silane coupling agent is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of excellent mechanical strength and low water absorption, 3-methacryloyloxypropyltrimethoxysilane and 8-methacryloyloxyoctyltrimethoxysilane are preferred, and 8-methacryloyloxyoctyltrimethoxysilane is more preferred.

[0085] The amount of the silane coupling agent used is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and even more preferably 1% by mass or more and 5% by mass or less, based on the total amount of the inorganic material.

[0086] The particle size of the inorganic filler is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of excellent mechanical strength, however, the particle size is preferably 0.01 μm or more and 100 μm or less, more preferably 0.05 μm or more and 70 μm or less, and even more preferably 0.1 μm or more and 50 μm or less.

[0087] Here, the particle size means the average particle size defined as the median size (d50).

[0088] The method for measuring the particle size of the inorganic filler is not particularly limited and can be appropriately selected depending on the purpose. For example, the particle size can be measured using a laser diffraction particle size distribution analyzer.

[0089] The content of the inorganic filler is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 70% by mass or more and 90% by mass or less, more preferably 72% by mass or more and 85% by mass or less, and even more preferably 75% by mass or more and 82% by mass or less, relative to the total amount of the dental polymerizable composition.

[0090] When the content of the inorganic filler is 70% by mass or more based on the total amount of the dental polymerizable composition, sufficient mechanical strength can be obtained.

[0091] When the content of the inorganic filler is 90 mass% or less relative to the total amount of the dental polymerizable composition, an increase in viscosity of the dental polymerizable composition can be suppressed, and the generation of bubbles when the dental polymerizable composition is hardened can be suppressed.

[0092] <Other Components> The other components are not particularly limited and can be appropriately selected within a range that does not impair the effects of the present invention. Examples thereof include a polymerization initiator, a polymerization accelerator, a polymerization inhibitor, a chain transfer agent, a filler (excluding the above-mentioned inorganic filler), a colorant, a pigment, a fluorescent agent, an antibacterial agent, etc.

[0093] Polymerization Initiator Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide.

[0094] The polymerization initiator may be used alone or in combination of two or more kinds.

[0095] The content of the polymerization initiator is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.005% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 5% by mass or less, and even more preferably 0.1% by mass or more and 3% by mass or less, relative to the total amount of the dental polymerizable composition.

[0096] When the content of the polymerization initiator is 0.005% by mass or more and 10% by mass or less relative to the total amount of the dental polymerizable composition, the polymerization efficiency when the dental polymerizable composition is cured is improved.

[0097] Filler Examples of fillers include inorganic fillers other than the above-mentioned inorganic fillers, such as silica zirconia and silica alumina, organic-inorganic composite fillers, and cluster fillers. It is preferable to use fillers that have been hydrophobized. A silane coupling agent such as 3-methacryloyloxypropyltrimethoxysilane can be used to hydrophobize the filler.

[0098] Pigments Examples of pigments include iron oxide and titanium oxide.

[0099] -Fluorescent Agent- Examples of the fluorescent agent include diethyl-2,5-dihydroxyterephthalate.

[0100] <Method for producing dental polymerizable composition> The method for producing the dental polymerizable composition is not particularly limited and can be appropriately selected depending on the purpose. For example, the dental polymerizable composition can be produced by mixing the various materials described above using a planetary mixer or a double planetary mixer.

[0101] The dental polymerizable composition has excellent mechanical strength and low water absorption, and therefore can be used in various dental materials.

[0102] Examples of dental materials include resin materials for dental cutting, composite resins for dental fillings, dental hard resins, dental surface lubricant hardeners, temporary dental restorative materials, dental filling materials, dental cements, dental adhesives (including primers for bonding crown restorations), dental primers, and tooth surface coating materials.

[0103] Among these, it can be suitably used as a resin material for dental cutting.

[0104] (Resin Material for Dental Cutting) The resin material for dental cutting of the present invention is obtained by polymerizing and curing a dental polymerizable composition.

[0105] The dental polymerizable composition may be any of those described in the above section (Dental polymerizable composition).

[0106] The method for polymerizing and curing the dental polymerizable composition is not particularly limited and can be appropriately selected depending on the purpose. Examples of the method include thermal polymerization, chemical polymerization, and photopolymerization.

[0107] The resin material for dental cutting of this embodiment uses the dental polymerizable composition of this embodiment, and therefore the effects of the dental polymerizable composition can be obtained, that is, a cured product (resin material for dental cutting) that has excellent mechanical strength and low water absorbency can be obtained.

[0108] (Method for Producing a Resin Material for Dental Cutting) The method for producing a resin material for dental cutting of the present invention includes a step of polymerizing and curing a dental polymerizable composition.

[0109] The dental polymerizable composition may be any of those described in the above section (Dental polymerizable composition).

[0110] The method for polymerizing and curing the dental polymerizable composition is not particularly limited and can be appropriately selected depending on the purpose. Examples of the method include thermal polymerization, chemical polymerization, and photopolymerization.

[0111] The polymerization conditions for polymerizing and curing the dental polymerizable composition are not particularly limited and can be appropriately selected depending on the purpose.

[0112] The polymerization temperature is preferably 50°C or higher and 200°C or lower, more preferably 80°C or higher and 180°C or lower, and even more preferably 110°C or higher and 150°C or lower.

[0113] The polymerization time is preferably from 20 minutes to 360 minutes, more preferably from 60 minutes to 240 minutes, and even more preferably from 100 minutes to 180 minutes.

[0114] The polymerization of the dental polymerizable composition may be carried out under pressure. In this case, the pressure is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.0 MPa or more and 10.0 MPa or less, more preferably 2.0 MPa or more and 8.0 MPa or less, and even more preferably 3.0 MPa or more and 5.0 MPa or less.

[0115] The method for producing a resin material for dental cutting according to the present embodiment uses the dental polymerizable composition of the present embodiment, and therefore the effects of the dental polymerizable composition can be obtained, i.e., a cured product (a resin material for dental cutting) that has excellent mechanical strength and low water absorption can be obtained.

[0116] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, parts mean parts by mass and % means % by mass.

[0117] (Examples 1 to 13 and Comparative Examples 1 to 7) Based on the materials and compositions shown in Tables 1 to 3, various materials were mixed using a magnetic stirrer to obtain a monomer liquid.

[0118] Pastes were prepared by mixing the monomer liquid and inorganic filler (fine silica powder + silane-treated glass) in a planetary mixer (or double planetary mixer) at the blending ratios [mass %] shown in Tables 4 to 6. These pastes were filled into a molding container and polymerized and cured for 60 to 180 minutes at 100°C to 130°C under a nitrogen pressure of 1.0 MPa to 5.0 MPa, to obtain the cured block products of Examples 1 to 13 and Comparative Examples 1 to 7.

[0119] The fine silica powder used was AEROSIL (registered trademark) R812 (fine silica powder, manufactured by Nippon Aerosil Co., Ltd.).

[0120] [Evaluation of Mechanical Strength] Test pieces measuring 1.2 mm × 4.0 mm × 14.0 mm were cut out from each of the cured blocks using a diamond cutter, and each surface of the test pieces was polished with P2000 waterproof abrasive paper. A three-point bending test was performed using a universal testing machine (AG-Xplus, manufactured by Shimadzu Corporation) under the conditions of a support distance of 12 mm and a crosshead speed of 1.0 mm / min, to measure the three-point bending strength.

[0121] The three-point bending strength was calculated according to the following formula (7).

[0122] In formula (7), F is the maximum load [N] measured in the bending test, S is the distance between supports [mm], b is the width [mm] of the test piece measured immediately before the test, and h is the thickness [mm] of the test piece measured immediately before the test. The three-point bending strength was evaluated as good if it was 310 MPa or more, and poor if it was less than 310 MPa. The results are shown in Tables 4 to 6.

[0123] [Evaluation of Water Absorbency] Test pieces measuring 9.0 mm x 14.0 mm x 1.0 mm were cut out from each of the cured block bodies using a diamond cutter, and each surface of the test piece was polished to a high gloss using alumina polishing powder and felt.

[0124] a) The obtained test pieces were stored in a desiccator set at 37±1° C. in an incubator.

[0125] b) After 22 hours, the specimen was removed and stored in another desiccator maintained at 23±2° C. for 2 hours. It was then weighed to the nearest 0.1 mg, and the drying procedure was continued and the measurement repeated until the mass loss of the specimen was less than 0.1 mg within 24 hours.

[0126] c) The test piece was stored in 20 mL of water at 37±1°C for 7 days, then removed, washed with water, and water droplets on the surface were removed using white filter paper. After that, it was shaken in the air for 15 seconds and weighed 1 minute after being removed from the water. This mass was measured as m １ It was decided.

[0127] d) After weighing, the final mass of the test specimen is determined by the procedures a) and b) again by the method m ２ It was decided.

[0128] e) The water absorption amount of each test piece was calculated according to the following formula (8).

[0129] In addition, in the formula (8), w ｓｐ is the water absorption amount (μg / mm ３ ), m １ is the mass (μg) of the test piece after storage in water for 7 days, m ２ is the mass (μg) of the test piece dried again after storage in water, and V is the volume (mm ３ ) is shown.

[0130]

[0131] The calculated water absorption was 20 μg / mm ３ 20 μg / mm ３ The results are shown in Tables 4 to 6.

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138] As can be seen from Tables 1 to 6, the resin blocks obtained using dental polymerizable compositions containing a first polymerizable monomer, a second polymerizable monomer, and an inorganic filler had good three-point bending strength and low water absorption (Examples 1 to 13).

[0139] In contrast, as can be seen from Tables 1 to 6, the resin blocks obtained using dental polymerizable compositions that did not contain the second polymerizable monomer were evaluated as poor in water absorbency (Comparative Examples 1 to 4).

[0140] Furthermore, from Tables 1 to 6, the resin blocks obtained using dental polymerizable compositions that did not contain the first polymerizable monomer were poor in durability (Comparative Examples 5 to 7).

[0141] Although the embodiments of the present invention have been described above, the present invention is not limited to the specific embodiments, and various modifications and changes are possible within the scope of the invention described in the claims.

[0142] The present invention includes, for example, the following aspects.

[0143] <1> A dental polymerizable composition comprising a first polymerizable monomer, a second polymerizable monomer, and an inorganic filler, wherein the first polymerizable monomer has only one group selected from the group consisting of a urethane group, a urea group, and a carbonate group, and the second polymerizable monomer has a structure represented by the following general formula (1) or a structure represented by the following general formula (2):

[0144] (In general formula (1), Y １ is an aromatic hydrocarbon group which may contain a heteroatom, and R １１ and R １２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X １１ and X １２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; a is an integer of 1 to 4; b is a number of 1 to 30; c is an integer of 1 to 4; d is a number of 1 to 30; and the sum of b and d is a number of 2 to 31.

[0145] (In general formula (2), Z １ and Z ２ are each independently any one selected from the group consisting of a urethane group, a urea group, and a carbonate group; Y ２ is a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, and R ２１ and R ２２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ２１ and X ２２ may be different from each other within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; e is an integer of 1 to 4, f is a number of 1 to 10, g is an integer of 1 to 4, h is a number of 1 to 10, and the sum of f and h is a number of 2 to 11). <2> The dental polymerizable composition according to <1>, wherein the inorganic filler is an inorganic filler that has been subjected to a hydrophobic treatment with a silane coupling agent, and the silane coupling agent is 8-methacryloyloxyoctyltrimethoxysilane.

[0146] <3> The dental polymerizable composition according to <1> or <2>, wherein the content of the inorganic filler is 150 parts by mass or more and 900 parts by mass or less, relative to 100 parts by mass of the total amount of the first polymerizable monomer and the second polymerizable monomer.

[0147] <4> The dental polymerizable composition according to any one of <1> to <3>, wherein the second polymerizable monomer includes at least one selected from the group consisting of a structure represented by the following general formula (3) and a structure represented by the following general formula (4):

[0148] (In general formula (3), R ３１ and R ３２ is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ３１ and X ３２may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; i is an integer of 1 to 3; j is a number of 1 to 9; k is an integer of 1 to 3; l is a number of 1 to 9; and the sum of j and l is a number of 2 to 10.

[0149] (In general formula (4), R ４１ and R ４２ is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ４１ and X ４２ may be different from one another within the same repeating unit, and each represents a hydrogen atom or an alkyl group having 5 or less carbon atoms; Y ４ represents a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, m is an integer of 1 to 3, n is a number of 1 to 5, o is an integer of 1 to 3, p is a number of 1 to 5, and the sum of n and p is a number of 2 to 8) <5> The dental polymerizable composition according to any one of <1> to <4>, wherein the second polymerizable monomer is at least one selected from 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 2.3), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 2.6), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 4), and di-2-(meth)acryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate.

[0150] <6> A dental resin material for cutting, characterized by being obtained by polymerizing and curing the dental polymerizable composition according to any one of <1> to <5>.

[0151] <7> A method for producing a resin material for dental cutting, comprising a step of polymerizing and curing the dental polymerizable composition according to any one of <1> to <6>.

[0152] The dental polymerizable composition according to any one of <1> to <5>, the resin material for dental cutting according to <6>, and the method for producing the resin material for dental cutting according to <7> can solve the various problems in the past and achieve the object of the present invention.

[0153] This application claims priority based on Japanese Patent Application No. 2024-051747, filed on March 27, 2024, the entire contents of which are incorporated herein by reference.

Claims

1. A dental polymerizable composition comprising a first polymerizable monomer, a second polymerizable monomer, and an inorganic filler, wherein the first polymerizable monomer has only one group selected from the group consisting of a urethane group, a urea group, and a carbonate group, and the second polymerizable monomer has a structure represented by the following general formula (1) or a structure represented by the following general formula (2): (In general formula (1), Y １ is an aromatic hydrocarbon group which may contain a heteroatom, and R １１ and R １２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X １１ and X １２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; a is an integer of 1 to 4; b is a number of 1 to 30; c is an integer of 1 to 4; d is a number of 1 to 30; and the sum of b and d is a number of 2 to 31. (In general formula (2), Z １ and Z ２ are each independently any one selected from the group consisting of a urethane group, a urea group, and a carbonate group; Y ２ is a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, and R ２１ and R ２２ are each independently a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ２１ and X ２２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; e is an integer of 1 to 4; f is a number of 1 to 10; g is an integer of 1 to 4; h is a number of 1 to 10; and the sum of f and h is a number of 2 to 11.

2. The dental polymerizable composition according to claim 1, wherein the inorganic filler is an inorganic filler that has been hydrophobized with a silane coupling agent, and the silane coupling agent is 8-methacryloyloxyoctyltrimethoxysilane.

3. A dental polymerizable composition according to claim 1 or 2, wherein the content of the inorganic filler is 150 parts by mass or more and 900 parts by mass or less per 100 parts by mass of the total amount of the first polymerizable monomer and the second polymerizable monomer.

4. The dental polymerizable composition according to any one of claims 1 to 3, wherein the second polymerizable monomer includes at least one selected from the group consisting of a structure represented by the following general formula (3) and a structure represented by the following general formula (4): (In general formula (3), R ３１ and R ３２ is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ３１ and X ３２ may be different within the same repeating unit and are a hydrogen atom or an alkyl group having 5 or less carbon atoms; i is an integer of 1 to 3; j is a number of 1 to 9; k is an integer of 1 to 3; l is a number of 1 to 9; and the sum of j and l is a number of 2 to 10. (In general formula (4), R ４１ and R ４２ is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X ４１ and X ４２ may be different from one another within the same repeating unit, and each represents a hydrogen atom or an alkyl group having 5 or less carbon atoms; Y ４ represents a chain hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, an alicyclic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, or an aromatic hydrocarbon group having 30 or less carbon atoms which may contain a heteroatom, m is an integer of 1 to 3, n is a number of 1 to 5, o is an integer of 1 to 3, p is a number of 1 to 5, and the sum of n and p is a number of 2 to 8).

5. The dental polymerizable composition according to any one of claims 1 to 4, wherein the second polymerizable monomer is at least one selected from 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 2.3), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 2.6), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 4), and di-2-(meth)acryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate.

6. A dental resin material for cutting, characterized by being obtained by polymerizing and curing the dental polymerizable composition according to any one of claims 1 to 5.

7. A method for producing a resin material for dental cutting, comprising the step of polymerizing and hardening the dental polymerizable composition according to any one of claims 1 to 5.

Images