Polymerizable composition for dental use, resin material for dental cutting processing, and method for producing the same

Abstract

The dental polymeric composition comprises a first polymeric monomer, a second polymeric monomer, and an inorganic filler, wherein the first polymeric monomer has only one group selected from urethane, urea, and carbonate groups, and the second polymeric monomer comprises a structure represented by general formula (1) or general formula (2). (In general formula (1), Y...) 1 It is an aromatic hydrocarbon group that may contain heteroatoms; R 11 and R 12 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 11 and X 12 In the same repeating unit, each can be different, being an alkyl group with 5 or fewer hydrogen or carbon atoms; a is an integer from 1 to 4; b is a number from 1 to 30; c is an integer from 1 to 4; d is a number from 1 to 30; the sum of b and d is a number from 2 to 31) (in general formula (2), Z 1 and Z 2 Each is independently selected from urethane, urea, and carbonate groups; Y 2 It can be a chain hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, an alicyclic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, or an aromatic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms; R 21 and R 22 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 21 and X 22 Within the same repeating unit, each element can be different, consisting of hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; e is an integer from 1 to 4; f is a number from 1 to 10; g is an integer from 1 to 4; h is a number from 1 to 10; the sum of f and h is a number from 2 to 11.

Description

Technical Field

[0001] This invention relates to polymeric compositions for dental use, resin materials for dental cutting, and methods for manufacturing the same. Background Technology

[0002] In recent years, CAD / CAM equipment has been used to design dental crowns, bridges, and other restorations on a computer screen and then manufacture them through machining. This CAD / CAM equipment allows for the production of high-quality dental restorations in a short time.

[0003] In the cutting process of dental restorations, a dental cutting resin material is used as the material before the shape is cut out (see, for example, Patent Document 1).

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent No. 6739809 Summary of the Invention The problem that the invention aims to solve The dental cutting resin material described in Patent Document 1 has the problem of deterioration due to absorption of moisture from the oral cavity. Furthermore, as a dental cutting resin material used in the manufacture of dental restorations, it is desirable to have excellent mechanical strength to ensure stability within the oral cavity.

[0005] Therefore, the object of the present invention is to provide a dental polymeric composition that can form a dental cutting resin material with excellent mechanical strength and low water absorption.

[0006] Methods for solving problems As a means of solving the problem, the dental polymeric composition of the present invention is A dental polymeric composition comprising a first polymeric monomer, a second polymeric monomer, and an inorganic filling material. The first polymerizable monomer mentioned above has only one group selected from urethane, urea, and carbonate groups. The aforementioned second polymerizable monomer comprises a structure represented by the following general formula (1) or a structure represented by the following general formula (2).

[0007] [Chemistry 1] (In general formula (1), Y) 1 It is an aromatic hydrocarbon group that may contain heteroatoms; R 11 and R 12 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 11 and X12 Within the same repeating unit, each element can be different, consisting of alkyl groups with 5 or fewer hydrogen atoms or carbon atoms; a is an integer from 1 to 4; b is a number from 1 to 30; c is an integer from 1 to 4; d is a number from 1 to 30; the sum of b and d is a number from 2 to 31. [Chemistry 2] (In general formula (2), Z) 1 and Z 2 Each is independently selected from urethane, urea, and carbonate groups; Y 2 It can be a chain hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, an alicyclic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, or an aromatic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms; R 21 and R 22 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 21 and X 22 Within the same repeating unit, each element can be different, consisting of hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; e is an integer from 1 to 4; f is a number from 1 to 10; g is an integer from 1 to 4; h is a number from 1 to 10; the sum of f and h is a number from 2 to 11. The effects of the invention According to the present invention, a dental polymeric composition is provided that can form a dental cutting resin material with excellent mechanical strength and low water absorption. Detailed Implementation

[0008] The following describes the detailed contents of this invention.

[0009] (Polymeric Composition for Dental Use) The dental polymeric composition of the present invention comprises a first polymeric monomer, a second polymeric monomer, and an inorganic filler, and may also contain other polymeric monomers and other components as needed.

[0010] <First polymerizable monomer> The first polymerizable monomer in this invention has only one group selected from urethane, urea and carbonate (hereinafter sometimes simply referred to as urethane, etc.), and may have other groups as needed.

[0011] Furthermore, a first polymerizable monomer having only one urethane group or the like refers to a monomer having only one urethane group or the like, and not having two or more urethane groups or the like.

[0012] The first polymeric monomer imparts mechanical strength to the cured product formed by curing a dental polymeric composition.

[0013] The urethane group is represented by the -NHCOO- group. The urea group is represented by the -NHCONH- group. The carbonate group is represented by the -OCOO- group.

[0014] There are no particular restrictions on the first polymerizable monomer, which can be appropriately selected according to the purpose. For example, (meth)acrylates having only one urethane group can be cited.

[0015] Furthermore, in this specification, (meth)acrylate refers to a compound having methacryloyloxy and / or acryloyloxy (hereinafter referred to as (meth)acryloyloxy).

[0016] There are no particular limitations on (meth)acrylates having only one carbamate group, etc., and they can be appropriately selected according to the purpose, but (meth)acrylates having two or more (meth)acryloyloxy groups are preferred.

[0017] There are no particular restrictions on (meth)acrylates having only one urethane group, etc., and they can be appropriately selected according to the purpose, but are preferably represented by the following formula (1).

[0018] [Chemistry 3] (In formula (1), A1 and A2 are each independently an alkyl group with 3 or fewer carbon atoms on the side chain, which is either (meth)acryloyloxy or (meth)acrylamide; B is a carbamate group; R1 and R2 are each independently an alkyl group with 8 or fewer carbon atoms on the side chain, which is either (meth)acryloyloxy or (meth)acrylamide) Furthermore, in this specification, (meth)acrylamide group means methacrylamide group and / or acrylamide group. Additionally, acrylamide group indicates a substituent represented by -NHCO (CH=CH2).

[0019] In the above formula (1), the number of carbon atoms of the alkyl group on the (meth)acryloyloxy or (meth)acrylamide side chain of A1 and A2 is preferably 2 or less, and more preferably there is no alkyl group on the (meth)acryloyloxy or (meth)acrylamide side chain.

[0020] In the above formula (1), the number of carbon atoms of the alkyl groups of R1 and R2 is preferably 5 or less.

[0021] When the number of carbon atoms in the alkyl groups of R1 and R2 is 8 or less, the deformation of polymeric monomers such as those having only one urethane group is suppressed, thereby enabling sufficient mechanical strength to be obtained from the cured product obtained by curing the dental polymeric composition.

[0022] As specific examples of (meth)acrylates containing only one carbamate group, as represented by the above formula (1), examples include (meth)acrylates represented by the following formulas (2) to (6).

[0023] [Chemistry 4] The (meth)acrylate represented by the above formula (2) is sometimes referred to as mUDMA.

[0024] [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] The content of the first polymeric monomer is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of imparting high mechanical strength to the cured product of the above-mentioned dental polymeric composition, it is preferably 5% by mass or more and 50% by mass or less relative to the total amount of the above-mentioned dental polymeric composition.

[0025] There are no particular limitations on the analytical methods used to confirm whether the dental polymeric composition contains the first polymeric monomer mentioned above. The appropriate method can be selected according to the purpose. For example, it can be confirmed by nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), Raman spectroscopy, and mass spectrometry (MS).

[0026] As the first polymerizable monomer, either a suitably synthesized product or a commercially available product can be used.

[0027] <Second polymerizable monomer> The second polymerizable monomer in this invention comprises a structure represented by the following general formula (1) or a structure represented by the following general formula (2), and may also include other structures as needed.

[0028] The second polymerizable monomer imparts low water absorption to the cured product formed by curing the dental polymeric composition.

[0029] [Chemistry 9] (In general formula (1), Y) 1 It is an aromatic hydrocarbon group that may contain heteroatoms; R 11 and R 12 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 11 and X 12Within the same repeating unit, each element can be different, consisting of alkyl groups with 5 or fewer hydrogen atoms or carbon atoms; a is an integer from 1 to 4; b is a number from 1 to 30; c is an integer from 1 to 4; d is a number from 1 to 30; the sum of b and d is a number from 2 to 31. [Chemistry 10] (In general formula (2), Z) 1 and Z 2 Each is independently selected from urethane, urea, and carbonate groups; Y 2 It can be a chain hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, an alicyclic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, or an aromatic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms; R 21 and R 22 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 21 and X 22 Within the same repeating unit, each element can be different, consisting of hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; e is an integer from 1 to 4; f is a number from 1 to 10; g is an integer from 1 to 4; h is a number from 1 to 10; the sum of f and h is a number from 2 to 11. <<Structures represented by general formula (1)>> [Chemistry 11] (In general formula (1), Y) 1 It is an aromatic hydrocarbon group that may contain heteroatoms; R 11 and R 12 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 11 and X 12 Within the same repeating unit, each element can be different, consisting of alkyl groups with 5 or fewer hydrogen atoms or carbon atoms; a is an integer from 1 to 4; b is a number from 1 to 30; c is an integer from 1 to 4; d is a number from 1 to 30; the sum of b and d is a number from 2 to 31. In the above general formula (1), X 11 and X 12 Preferably, it contains hydrogen atoms or methyl groups.

[0030] In the above general formula (1), R 11 and R 12 Preferably, it contains hydrogen atoms or methyl groups.

[0031] In the above general formula (1), a is preferably an integer from 1 to 3.

[0032] In the above general formula (1), b is preferably a number from 1 to 15.

[0033] In the above general formula (1), c is preferably an integer from 1 to 3.

[0034] In the above general formula (1), d is preferably a number from 1 to 15.

[0035] In the above general formula (1), b and d are average values, and the sum of b and d is preferably a number between 2 and 18.

[0036] There are no particular restrictions on the aromatic hydrocarbon groups in the above general formula (1), which can be appropriately selected according to the purpose, but are preferably any structure represented by the following general formula (1-1).

[0037] [Chemistry 12] (In general formula (1-1), R) 23 R 24 R 25 R 26 R 27 and R 28 Each is an aliphatic hydrocarbon group containing heteroatoms, which is independently composed of hydrogen atoms or carbon atoms numbering 1 to 5 (preferably hydrogen atoms or methyl groups). Among these, the structure represented by the following general formula (1-2) is preferred.

[0038] [Chemistry 13] (In general formula (1-2), R) 23 R 24 R 25 R 26 R 27 and R 28 Each is an aliphatic hydrocarbon group containing heteroatoms, which is independently composed of hydrogen atoms or carbon atoms numbering 1 to 5 (preferably hydrogen atoms or methyl groups). <<Structures represented by general formula (2)>> [Chemistry 14] (In general formula (2), Z) 1 and Z 2 Each is independently selected from urethane, urea, and carbonate groups; Y 2 It can be a chain hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, an alicyclic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, or an aromatic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms; R 21 and R 22 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 21 and X 22Within the same repeating unit, each element can be different, consisting of hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; e is an integer from 1 to 4; f is a number from 1 to 10; g is an integer from 1 to 4; h is a number from 1 to 10; the sum of f and h is a number from 2 to 11. In the above general formula (2), X 21 and X 22 Preferably, it contains hydrogen atoms or methyl groups.

[0039] In the above general formula (2), R 21 and R 22 Preferably, it contains hydrogen atoms or methyl groups.

[0040] In the above general formula (2), e is preferably an integer from 1 to 3.

[0041] In the above general formula (2), f is preferably a number from 1 to 6.

[0042] In the above general formula (2), g is preferably an integer from 1 to 3.

[0043] In the above general formula (2), h is preferably a number from 1 to 6.

[0044] In the above general formula (2), f and h are average values, and the sum of f and h is preferably a number between 2 and 6.

[0045] There are no particular restrictions on the alicyclic hydrocarbon groups and aromatic hydrocarbon groups in the above general formula (2), and they can be appropriately selected according to the purpose, but it is preferred to use any structure represented by the following general formula (2-1).

[0046] [Chemistry 15] (In general formula (2-1), R) 33 R 34 R 35 R 36 R 37 R 38 and R 39 Each is an aliphatic hydrocarbon group containing heteroatoms, which is independently composed of hydrogen atoms or carbon atoms numbering 1 to 8 (preferably hydrogen atoms or methyl groups). As a second polymerizable monomer, from the viewpoint of having excellent hydrophobicity, it is preferred to include at least one of the structures represented by the following general formula (3) and the following general formula (4).

[0047] [Chemistry 16] (In general formula (3), R) 31 and R 32 It is an alkyl group having 3 or fewer hydrogen atoms; X 31 and X32 Within the same repeating unit, each element can be different, consisting of hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; i is an integer from 1 to 3; j is a number from 1 to 9; k is an integer from 1 to 3; l is a number from 1 to 9; the sum of j and l is a number from 2 to 10. [Chemistry 17] (In general formula (4), R) 41 and R 42 It is an alkyl group having 3 or fewer hydrogen atoms; X 41 and X 42 Within the same repeating unit, they can each differ, being either hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; Y 4 The following are listed: chain hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; alicyclic hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; or aromatic hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; m is an integer from 1 to 3; n is a number from 1 to 5; o is an integer from 1 to 3; p is a number from 1 to 5; the sum of n and p is a number from 2 to 8. <<Structures represented by general formula (3)>> [Chemistry 18] (In general formula (3), R) 31 and R 32 It is an alkyl group having 3 or fewer hydrogen atoms; X 31 and X 32 Within the same repeating unit, each element can be different, consisting of hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; i is an integer from 1 to 3; j is a number from 1 to 9; k is an integer from 1 to 3; l is a number from 1 to 9; the sum of j and l is a number from 2 to 10. In general formula (3), the numbers j and l are the average values, respectively.

[0048] Specific examples of polymerizable monomers containing structures represented by general formula (3) include 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average molar addition of oxyethylene: 2.3), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average molar addition of oxyethylene: 2.6, commonly known as: D-2.6E), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average molar addition of oxyethylene: 4), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average molar addition of oxyethylene: 10), etc.

[0049] There is no particular limitation on the average number of oxyethylene additions in the polymerizable monomer containing the structure represented by general formula (3), which can be appropriately selected according to the purpose, but is preferably 2 or more and 9 or less.

[0050] <<Structures represented by general formula (4)>> [Chemistry 19] (In general formula (4), R) 41 and R 42 It is an alkyl group having 3 or fewer hydrogen atoms; X 41 and X 42 Within the same repeating unit, they can each differ, being either hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; Y 4 The following are listed: chain hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; alicyclic hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; or aromatic hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; m is an integer from 1 to 3; n is a number from 1 to 5; o is an integer from 1 to 3; p is a number from 1 to 5; the sum of n and p is a number from 2 to 8. In general formula (4), the numbers n and p are the average values, respectively.

[0051] Specific examples of polymerizable monomers containing structures represented by general formula (4) include di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarboxylate (UDMA), etc.

[0052] The content of the second polymeric monomer is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of imparting excellent low water absorption to the cured product of the above-mentioned dental polymeric composition, it is preferably 0.5% by mass or more and 30% by mass or less relative to the total amount of the above-mentioned dental polymeric composition.

[0053] There are no particular limitations on the analytical methods used to confirm whether the dental polymeric composition contains the aforementioned second polymeric monomer. The appropriate method can be selected according to the purpose. For example, it can be confirmed by nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), Raman spectroscopy, and mass spectrometry (MS).

[0054] As a second polymerizable monomer, either a suitably synthesized product or a commercially available product can be used.

[0055] <Other polymerizable monomers> The other polymerizable monomers mentioned above are not particularly limited and can be appropriately selected within the scope of not impairing the effect of the present invention. Examples 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, tricyclodecanediethanol 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.

[0056] There are no particular restrictions on the content of the other polymerizable monomers mentioned above, and they can be appropriately selected within the scope of not impairing the effect of the present invention.

[0057] Other polymerizable monomers can be appropriately synthesized products or commercially available products.

[0058] <Inorganic filler> The aforementioned inorganic filler is preferably composed of inorganic materials and is preferably contained in a dental polymeric composition in particulate form.

[0059] There are no particular restrictions on inorganic fillers, and they can be selected appropriately according to the purpose. Examples include barium glass, strontium glass, fluoroaluminosilicate glass, and silica micro powder.

[0060] Inorganic fillers are preferably made from materials that have undergone hydrophobic treatment. Hydrophobic treatment of inorganic fillers can be achieved, for example, by using silane coupling agents.

[0061] There are no particular limitations on the silane coupling agent, and it can be appropriately selected according to the purpose. However, from the viewpoint of superior mechanical strength and low water absorption, 3-methacryloxypropyltrimethoxysilane and 8-methacryloxyoctyltrimethoxysilane are preferred, and 8-methacryloxyoctyltrimethoxysilane is more preferred.

[0062] There is no particular limitation on the amount of silane coupling agent used, and it can be appropriately selected according to the purpose. However, relative to the total amount of inorganic material, it 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.

[0063] There is no particular limitation on the particle size of the inorganic filler, which can be appropriately selected according to the purpose. However, from the viewpoint of excellent mechanical strength, it is preferred to be 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.

[0064] Here, particle size refers to the average particle size defined by the median diameter (d50).

[0065] There are no particular restrictions on the measurement method for inorganic filler particle size; it can be selected appropriately according to the purpose. For example, it can be measured by a laser diffraction particle size distribution measuring device.

[0066] There is no particular limitation on the content of inorganic filler, which can be appropriately selected according to the purpose, but it is preferably 70% by mass or more and 90% by mass or less relative to the total amount of the dental polymeric composition, 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.

[0067] Sufficient mechanical strength can be obtained when the content of inorganic filler is 70% or more by mass relative to the total amount of the dental polymeric composition.

[0068] When the content of inorganic filler is less than 90% by mass relative to the total amount of the dental polymeric composition, the increase in viscosity of the dental polymeric composition can be suppressed, and the generation of bubbles during the curing of the dental polymeric composition can be suppressed.

[0069] <Other Ingredients> Other components are not particularly limited and can be appropriately selected within the scope of not impairing the effect of the present invention. Examples include polymerization initiators, polymerization accelerators, polymerization inhibitors, chain transfer agents, fillers (excluding the above-mentioned inorganic fillers), colorants, pigments, fluorescent agents, antibacterial agents, etc.

[0070] -Polymerization initiator- Examples of polymerization initiators include organic peroxides such as benzoyl peroxide.

[0071] Polymerization initiators can be used alone or in combination with two or more.

[0072] There is no particular limitation on the content of the polymerization initiator, which can be appropriately selected according to the purpose, but it is preferably 0.005% by mass or more and 10% by mass or less relative to the total amount of the dental polymeric composition, 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.

[0073] 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 polymeric composition, the polymerization efficiency during curing of the dental polymeric composition will be improved.

[0074] -filler- Examples of fillers include inorganic fillers other than those mentioned above, such as silica-zirconia and silica-alumina, as well as organic-inorganic composite fillers and clustered fillers. Furthermore, fillers preferably use materials that have undergone hydrophobic treatment. Hydrophobic treatment of fillers can be achieved, for example, using silane coupling agents such as 3-methacryloyloxypropyltrimethoxysilane.

[0075] -pigment- Examples of pigments include iron oxide and titanium dioxide.

[0076] -Fluorescent agents- Examples of fluorescent agents include diethyl-2,5-dihydroxyterephthalate.

[0077] <Method for manufacturing polymeric compositions for dental use> There are no particular limitations on the manufacturing method of the dental polymeric composition, which can be appropriately selected according to the purpose. For example, it can be manufactured by mixing the various materials mentioned above using a rotary mixer or a dual planetary mixer.

[0078] Dental polymeric compositions have excellent mechanical strength and low water absorption, making them suitable for use in a variety of dental materials.

[0079] Examples of dental materials include resin materials for dental cutting and machining, composite resins for dental fillings, hard resins for dental use, dental surface lubricants and curing agents, temporary dental restorative materials, dental filling materials, dental cement, dental adhesives (including primers for bonding crown restorations), dental primers, and tooth surface coating materials.

[0080] Among these, resin materials suitable for dental cutting processes are available.

[0081] (Resin materials for dental cutting) The dental cutting resin material of the present invention is obtained by polymerizing and curing a dental polymeric composition.

[0082] Furthermore, regarding the polymeric composition for dental use, the materials described in the above-mentioned (polymeric compositions for dental use) item may be used.

[0083] There are no particular restrictions on the methods for polymerizing and curing dental polymeric compositions; appropriate methods can be selected according to the purpose, such as heating polymerization, chemical polymerization, photopolymerization, etc.

[0084] In the dental cutting resin material of this embodiment, since the dental polymeric composition of this embodiment is used, the effects of the dental polymeric composition can be obtained. That is, a cured product (dental cutting resin material) with excellent mechanical strength and low water absorption can be obtained.

[0085] (Manufacturing method of resin material for dental cutting) The method for manufacturing a dental cutting resin material of the present invention includes a step of polymerizing and curing a dental polymeric composition.

[0086] Furthermore, regarding the polymeric composition for dental use, the materials described in the above-mentioned (polymeric compositions for dental use) item may be used.

[0087] There are no particular restrictions on the methods for polymerizing and curing dental polymeric compositions; appropriate methods can be selected according to the purpose, such as heating polymerization, chemical polymerization, photopolymerization, etc.

[0088] There are no particular restrictions on the polymerization conditions used to polymerize and cure the dental polymeric composition; they can be appropriately selected according to the purpose.

[0089] 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.

[0090] The polymerization time is preferably 20 minutes or more and 360 minutes or less, more preferably 60 minutes or more and 240 minutes or less, and even more preferably 100 minutes or more and 180 minutes or less.

[0091] The polymerization of the dental polymeric composition can also be carried out under pressure. There are no particular limitations on the pressure in this case, and it can be appropriately selected according to the purpose, but it 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.

[0092] In the method for manufacturing the dental cutting resin material of this embodiment, since the dental polymeric composition of this embodiment is used, the effects of the dental polymeric composition can be obtained. That is, a cured product (dental cutting resin material) with excellent mechanical strength and low water absorption can be obtained.

[0093] Example The present invention is illustrated below with examples and comparative examples, but the present invention is not limited to these examples in any way. Furthermore, in the following examples and comparative examples, unless otherwise stated, "parts" refers to parts by mass and "%" refers to percentages by mass.

[0094] (Examples 1-13 and Comparative Examples 1-7) Based on the materials and compositions shown in Tables 1-3, various materials were mixed using a magnetic stirrer to obtain a monomeric liquid.

[0095] The monomer liquid and inorganic filler (silica micro powder + silane-treated glass) were mixed in a rotary mixer (or a double planetary mixer) at the mixing ratios [mass %] shown in Tables 4-6 to prepare a paste. The paste was filled into a molding container and polymerized and cured at 100°C-130°C and 1.0 MPa-5.0 MPa nitrogen pressure for 60-180 minutes to obtain the block-shaped cured bodies of Examples 1-13 and Comparative Examples 1-7.

[0096] In addition, AEROSIL (registered trademark) R812 (silica micro powder, manufactured by AEROSIL Corporation of Japan) was used as the silica micro powder.

[0097] [Evaluation of Mechanical Strength] Using a diamond cutter, 1.2 mm × 4.0 mm × 14.0 mm test pieces were cut from each block of solidified material, and all surfaces of the test pieces were polished with P2000 water-resistant sandpaper. A three-point bending test was performed using a universal testing machine (Shimadzu AG-Xplus) with a support distance of 12 mm and a crosshead speed of 1.0 mm / min to measure the three-point bending strength.

[0098] The three-point bending strength is calculated according to the following formula (7).

[0099] [Number 1] In equation (7), F is the maximum load measured in the bending test [N], S is the distance between the supports [mm], b is the width of the specimen measured immediately before the test [mm], and h is the thickness of the specimen measured immediately before the test [mm]. Evaluation of three-point bending strength: a three-point bending strength of 310 MPa or higher is considered good, and a strength less than 310 MPa is considered poor. The results are recorded in Tables 4 to 6.

[0100] [Evaluation of water absorbency] Using a diamond cutter, test pieces of 9.0 mm × 14.0 mm × 1.0 mm were cut from each block of solidified material, and each surface of the test pieces was polished with alumina polishing powder and felt.

[0101] a) Store the obtained test pieces in a desiccator set at 37±1℃ in a thermostat.

[0102] b) After 22 hours, remove the test piece and store it in another desiccator maintained at 23±2℃ for 2 hours. Then, weigh it in units of 0.1 mg and continue the drying procedure, repeating the measurement, until the mass reduction of the test piece is less than 0.1 mg within 24 hours.

[0103] c) After storing the sample in 20 mL of water at 37±1℃ for 7 days, remove it, wash it with water, and remove surface water droplets with white filter paper. Then, shake it in the air for 15 seconds and weigh it 1 minute after removing it from the water. Record this mass as m1.

[0104] d) After weighing, follow steps a) and b) to record the final mass of the dried sample as m2.

[0105] e) The water absorption of each test piece is calculated according to the following formula (8).

[0106] Furthermore, in equation (8), w sp Indicates water absorption (μg / mm) 3 m1 represents the mass (μg) of the sample after 7 days of water storage, m2 represents the mass (μg) of the sample after water storage and subsequent drying, and V represents the volume (mm²) of the sample. 3 ).

[0107] [Number 2] The calculated water absorption rate is 20 μg / mm. 3 The following is considered good: exceeding 20 μg / mm 3 The condition was determined to be unsatisfactory. The results are recorded in Tables 4-6.

[0108] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] As shown in Tables 1-6, the resin blocks obtained by using a dental polymeric composition containing a first polymeric monomer, a second polymeric monomer, and an inorganic filler have good three-point bending strength and low water absorption (Examples 1-13).

[0109] In contrast, as shown in Tables 1-6, the resin blocks obtained using dental polymeric compositions that do not contain a second polymeric monomer have poor water absorption (Comparative Examples 1-4).

[0110] Furthermore, as shown in Tables 1-6, the resin blocks obtained using dental polymeric compositions that do not contain the first polymeric monomer have poor durability (Comparative Examples 5-7).

[0111] The above describes the embodiments of the present invention, but the present invention is not limited to the specific embodiments. Various modifications and alterations can be made within the scope of the invention as described in the claims.

[0112] As an example of the present invention, the following can be cited.

[0113] <1> A dental polymeric composition comprising a first polymeric monomer, a second polymeric monomer, and an inorganic filling material, characterized in that, The first polymerizable monomer mentioned above has only one group selected from urethane, urea, and carbonate groups. The aforementioned second polymerizable monomer comprises a structure represented by the following general formula (1) or a structure represented by the following general formula (2).

[0114] [Chemistry 20] (In general formula (1), Y) 1 It is an aromatic hydrocarbon group that may contain heteroatoms; R 11 and R 12 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 11 and X 12 Within the same repeating unit, each element can be different, consisting of alkyl groups with 5 or fewer hydrogen atoms or carbon atoms; a is an integer from 1 to 4; b is a number from 1 to 30; c is an integer from 1 to 4; d is a number from 1 to 30; the sum of b and d is a number from 2 to 31. [Chemistry 21] (In general formula (2), Z) 1 and Z 2 Each is independently selected from urethane, urea, and carbonate groups; Y 2 It can be a chain hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, an alicyclic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, or an aromatic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms; R 21 and R 22 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms; X 21 and X 22Within the same repeating unit, each element can be different, consisting of hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; e is an integer from 1 to 4; f is a number from 1 to 10; g is an integer from 1 to 4; h is a number from 1 to 10; the sum of f and h is a number from 2 to 11. <2> according to <1> The aforementioned polymeric composition for dental use, wherein the inorganic filling material is an inorganic filling material that has been hydrophobically treated with a silane coupling agent. The aforementioned silane coupling agent is 8-methacryloyloxyoctyltrimethoxysilane.

[0115] <3> according to <1> or <2> The aforementioned dental polymeric composition, wherein, relative to 100 parts by mass of the first polymeric monomer and the second polymeric monomer, the content of the inorganic filler is 150 parts by mass or more and 900 parts by mass or less.

[0116] <4> according to <1> to <3> The dental polymeric composition according to any one of the following, wherein the second polymeric monomer comprises at least one selected from the structure represented by the following general formula (3) and the structure represented by the following general formula (4).

[0117] [Chemistry 22] (In general formula (3), R) 31 and R 32 It is an alkyl group having 3 or fewer hydrogen atoms; X 31 and X 32 Within the same repeating unit, each element can be different, consisting of hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; i is an integer from 1 to 3; j is a number from 1 to 9; k is an integer from 1 to 3; l is a number from 1 to 9; the sum of j and l is a number from 2 to 10. [Chemistry 23] (In general formula (4), R) 41 and R 42 It is an alkyl group having 3 or fewer hydrogen atoms; X 41 and X 42 Within the same repeating unit, they can each differ, being either hydrogen atoms or alkyl groups with 5 or fewer carbon atoms; Y 4 The following are listed: chain hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; alicyclic hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; or aromatic hydrocarbon groups with 30 or fewer carbon atoms that may contain heteroatoms; m is an integer from 1 to 3; n is a number from 1 to 5; o is an integer from 1 to 3; p is a number from 1 to 5; the sum of n and p is a number from 2 to 8. <5> according to <1> to <4> The dental polymeric composition according to any one of the following, wherein the second polymeric monomer is at least one selected from 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average molar addition of oxyethylene: 2.3), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average molar addition of oxyethylene: 2.6), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average molar addition of oxyethylene: 4), and di-2-(meth)acryloyloxyethyl-2,2,4-trimethylhexamethylenedicarbamate.

[0118] <6> A resin material for dental cutting, characterized in that it is made by... <1> to <5> The dental polymeric composition described in any one of the above is polymerized and cured.

[0119] <7> A method for manufacturing a resin material for dental cutting, characterized by comprising making <1> to <6> The process of polymerizing and curing the dental polymeric composition as described in any one of the above.

[0120] according to <1> to <5> The dental polymeric composition described in any one of the following statements, <6> The aforementioned dental cutting resin material, and <7> The method for manufacturing resin materials for dental cutting can solve various problems in the prior art, thereby achieving the purpose of this invention.

[0121] 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 polymeric composition comprising a first polymeric monomer, a second polymeric monomer, and an inorganic filling material, characterized in that, The first polymerizable monomer has only one group selected from the group consisting of urethane, urea, and carbonate groups. The second polymerizable monomer comprises 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 R is an aromatic hydrocarbon group that may contain heteroatoms. 11 and R 12 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms, X 11 and X 12 Within the same repeating unit, each element can be different, and can be an alkyl group with 5 or fewer hydrogen atoms or carbon atoms. 'a' is an integer from 1 to 4, 'b' is a number from 1 to 30, 'c' is an integer from 1 to 4, and 'd' is a number from 1 to 30. The sum of 'b' and 'd' is a number from 2 to 31. In general formula (2), Z 1 and Z 2 Each independently selected from the group consisting of urethane, urea, and carbonate groups, Y 2 R is a chain hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms; an alicyclic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms; or an aromatic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms. 21 and R 22 Each is independently a hydrogen atom or an alkyl group having 3 or fewer carbon atoms, X 21 and X 22 Each element in the same repeating unit can be different, and can be an alkyl group with 5 or fewer hydrogen atoms or carbon atoms. e is an integer from 1 to 4, f is a number from 1 to 10, g is an integer from 1 to 4, h is a number from 1 to 10, and the sum of f and h is a number from 2 to 11.

2. The dental polymeric composition according to claim 1, wherein the inorganic filling material is an inorganic filling material that has been hydrophobically treated with a silane coupling agent. The silane coupling agent is 8-methacryloyloxyoctyltrimethoxysilane.

3. The dental polymeric 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 relative to the total mass of the first polymeric monomer and the second polymeric monomer of 100 parts by mass.

4. The dental polymeric composition according to any one of claims 1 to 3, wherein the second polymeric monomer comprises at least one selected from the structure represented by general formula (3) and the structure represented by general formula (4). In general formula (3), R 31 and R 32 X is an alkyl group having 3 or fewer hydrogen atoms or carbon atoms. 31 and X 32 Within the same repeating unit, each element can be different, and each can be an alkyl group with 5 or fewer hydrogen atoms or carbon atoms. i is an integer from 1 to 3, j is a number from 1 to 9, k is an integer from 1 to 3, l is a number from 1 to 9, and the sum of j and l is a number from 2 to 10. In general formula (4), R 41 and R 42 X is an alkyl group having 3 or fewer hydrogen atoms or carbon atoms. 41 and X 42 Each can be different within the same repeating unit, being either a hydrogen atom or an alkyl group having 5 or fewer carbon atoms, Y 4 It is a chain hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, an alicyclic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, or an aromatic hydrocarbon group with 30 or fewer carbon atoms and may contain heteroatoms, where m is an integer from 1 to 3, n is a number from 1 to 5, o is an integer from 1 to 3, p is a number from 1 to 5, and the sum of n and p is a number from 2 to 8.

5. The dental polymeric composition according to any one of claims 1 to 4, wherein the second polymeric monomer is selected from at least one of 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane with an average molar addition of 2.3 oxyvinyl groups, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane with an average molar addition of 2.6 oxyvinyl groups, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane with an average molar addition of 4 oxyvinyl groups, and di-2-(meth)acryloyloxyethyl-2,2,4-trimethylhexamethylenedicarbamate.

6. A resin material for dental cutting, characterized in that, It is formed by polymerizing and curing the dental polymeric composition according to any one of claims 1 to 5.

7. A method for manufacturing a resin material for dental cutting, characterized in that, The process includes a step of polymerizing and curing the dental polymeric composition according to any one of claims 1 to 5.

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