Dental hardening composition that provides high mechanical strength

Abstract

To provide a dental curable composition that can obtain high mechanical strength after hardening. [Solution] A dental curable composition comprising a silane coupling material represented by formula (1) and / or an inorganic filler surface-treated with a silane coupling material represented by formula (1). [Formula (1)] TIFF2026060965000018.tif6464

Description

Technical Field

[0001] The present invention relates to a dental curable composition containing a radically polymerizable coupling agent having a methacrylamide structure.

Background Art

[0002] In dental treatment, dental curable compositions composed of a polymerizable monomer, an inorganic filler, and a polymerization initiator are widely used. These are generally called dental composite resins and are used for various purposes such as direct restorative materials for tooth defects due to dental caries, etc., crown prosthetic restorative materials such as inlays, crowns, and bridges, abutment tooth construction materials for crown defect parts, and block materials for dental CAD / CAM.

[0003] Generally, (meth)acrylic acid derivative monomers such as methyl methacrylate, triethylene glycol dimethacrylate, and urethane dimethacrylate are used in dental composite resins. In the free radical polymerization (hereinafter referred to as radical polymerization) of vinyl monomers such as these (meth)acrylic acid derivative monomers, the carbon-carbon double bond cleaves and becomes a single bond, forming a high molecular weight polymer and curing. In composite resins, not only vinyl monomers but also inorganic fillers are added for the purpose of improving mechanical strength. Generally, these inorganic fillers are surface-treated with a silane coupling material having a polymerizable group to improve wettability and mechanical strength. Conventionally, γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as KBM-503) has been widely used as a silane coupling material in the dental field. When an inorganic filler surface-treated with this compound is used, there is a problem that hydrolysis easily progresses due to low hydrophobicity, resulting in low durability of the material. Therefore, it had the drawback that sufficient mechanical strength could not be obtained.

[0004] Therefore, in order to improve the durability and filling rate of the material, methods have been proposed such as using a radical polymerizable silane coupling material with a cyclic compound as its backbone (Patent Document 1), using a silane coupling material having many polymerizable groups (Patent Document 2), using a silane coupling material with a long alkyl chain (Patent Document 3), using a silane coupling material having a hydroxyl group and a urethane group (Patent Document 4), using a silane coupling material having an epoxy ring and a urethane group (Patent Document 5), using a silane coupling material having a fluorine-containing organic group (Patent Document 6), using two types of silane coupling materials in combination (Patent Documents 7 and 8), and using a radical polymerizable silane coupling material having a urethane bond (Patent Documents 9, 10, 11 and 12). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 7118549 [Patent Document 2] Patent No. 5416447 [Patent Document 3] Patent No. 6220723 [Patent Document 4] Patent No. 7104490 [Patent Document 5] Patent No. 7104489 [Patent Document 6] Patent No. 7093628 [Patent Document 7] Patent No. 6220723 [Patent Document 8] Patent No. 6793241 [Patent Document 9] Patent No. 6841915 [Patent Document 10] Patent No. 7104488 [Patent Document 11] Patent No. 7104487 [Patent Document 12] Patent No. 7104486 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, when the methods described in Patent Documents 1 to 12 were applied to dental cutting resin hardened bodies and the like, there was room for improvement in mechanical strength.

[0007] The present invention aims to provide a dental curable composition that can obtain high mechanical strength after curing. [Means for solving the problem]

[0008] As a result of diligent research by the inventors, it was discovered that surface treatment of an inorganic filler with a silane coupling material represented by the chemical structural formula (1) below provides high affinity for radical polymerizable monomers, particularly radical polymerizable monomers containing urethane bonds and hydrogen bonds, and high dispersibility of the inorganic filler. This makes it possible to provide high mechanical strength when used in dental curable compositions. The present invention is based on the above findings. [Formula (1)] [ka]

[0009] The present invention provides a dental curable composition comprising a silane coupling material represented by formula (1) and / or an inorganic filler surface-treated with a silane coupling material represented by the following formula (1). [Formula (1)] [ka] [Effects of the Invention]

[0010] According to the dental curable composition of the present invention, high mechanical strength can be obtained after curing. [Modes for carrying out the invention]

[0011] The dental curable composition of the present invention contains a silane coupling agent represented by formula (1) and / or an inorganic filler surface-treated with the silane coupling agent represented by formula (1).

[0012] By surface-treating the inorganic filler with the silane coupling agent represented by formula (1), high affinity for a polymerizable monomer, particularly a radical polymerizable monomer having a urethane bond or a hydrogen bond, and high dispersibility of the inorganic filler are exhibited. As a result, high mechanical strength and flexibility are imparted to the cured body of the dental curable composition.

[0013] This high affinity effect is remarkably exhibited when the radical polymerizable monomer has a urethane bond or a hydrogen bond. This is considered to be due to the presence of a nitrogen atom and an amide bond in formula (1).

[0014] [Formula (1)] [Chemical formula]

[0015] The inorganic filler surface-treated with the silane coupling agent represented by formula (1) is considered to have nitrogen atoms and amide bonds introduced on its surface and to exhibit high affinity with a radical polymerizable monomer having a urethane bond or a hydrogen bond.

[0016] Also, it is considered that the presence of the amide bond forms a hydrogen bond between amide groups, strengthening the bond between the inorganic fillers surface-treated with the silane coupling agent. In the present invention, high filling of the inorganic filler becomes possible, and as a result, high mechanical strength can be achieved.

[0017] The dental curable composition of the present invention can contain an inorganic filler surface-treated with the silane coupling agent represented by formula (1).

[0018] In the dental curable composition of the present invention, the amount of silane coupling material used in surface treatment can be 0.1 to 20 parts by weight per 100 parts by weight of inorganic filler.

[0019] The dental curable composition of the present invention may contain an inorganic filler surface-treated with a silane coupling agent represented by formula (1) in an amount of 1 to 90 parts by weight per 100 parts by weight of the total dental curable composition.

[0020] The dental curable composition of the present invention may further contain a radical polymerizable monomer and a polymerization initiator.

[0021] The dental curable composition of the present invention may further include an inorganic filler surface-treated with a surface treatment agent other than the silane coupling agent represented by formula (1).

[0022] The dental curable composition of the present invention may have a urethane bond in its radical polymerizable monomer.

[0023] The dental curable composition of the present invention may have a radical polymerizable monomer having one or more hydroxyl groups and two or more polymerizable groups.

[0024] The dental curable composition of the present invention may have a monomer represented by formula (2) as a radical polymerizable monomer. [Formula (2)] [ka]

[0025] The dental curable composition of the present invention may contain a radical polymerizable monomer having a compound represented by formula (2) in an amount of 1 to 10 parts by weight per 100 parts by weight of the total dental curable composition.

[0026] The dental curable composition of the present invention may have a weight ratio of a silane coupling agent represented by formula (1) and a radical polymerizable monomer having a compound represented by formula (2) in the range of 1:0.5 to 1:20.

[0027] The dental curable composition of the present invention can be a spherical nanofiller having an average particle size of 0.01 to 1 μm, in which the inorganic filler surface-treated with a silane coupling material represented by formula (1) is located.

[0028] The dental curable composition of the present invention can be a crushed inorganic filler in which the inorganic filler surface-treated with a silane coupling agent represented by formula (1) has an average particle size of 0.01 to 10 μm.

[0029] The dental curable composition of the present invention can be an aggregated inorganic filler in which the inorganic filler surface-treated with a silane coupling agent represented by formula (1) has an average particle size of 0.01 to 10 μm.

[0030] The dental curable composition of the present invention may consist of aggregated inorganic fillers comprising SiO2: 50-99% by weight and ZrO2: 1-50% by weight.

[0031] The dental curable composition of the present invention can have a polymerization initiator whose 10-hour half-life temperature is between 70°C and 170°C.

[0032] The dental curable composition of the present invention can have a cured body that exhibits a flexural strength of 300 MPa or more after being stored in water at 37°C for one week.

[0033] The dental curable composition of the present invention can have a cured body with a flexural modulus of 20 GPa or more after being stored in water at 37°C for one week.

[0034] The dental curable composition of the present invention can be used in the manufacture of dental cutting resin curing bodies.

[0035] The dental curing composition of the present invention can be used in the manufacture of dental composite resins.

[0036] The dental curable composition of the present invention can be used as a dental curable composition for 3D printers.

[0037] The present invention provides an inorganic filler surface-treated with a silane coupling material represented by formula (1). [Formula (1)] [ka]

[0038] [Silane coupling material represented by formula (1)] The silane coupling material used in the present invention has a methacrylamide structure, specifically the structure shown in formula (1). In the present invention, the silane coupling material represented by formula (1) may be used alone or in combination with other surface treatment agents for surface treatment. Other surface treatment agents are not particularly limited, but include 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, titanium acetylacetonate, and zirconium ethyl acetoacetate. [Formula (1)] [ka]

[0039] The dental curable composition of the present invention may contain the silane coupling material represented by formula (1) in its pre-surface treatment form, i.e., the silane coupling material represented by formula (1) itself, or in its post-surface treatment form, i.e., an inorganic filler surface-treated with the silane coupling material represented by formula (1). The dental curable composition of the present invention may contain both the silane coupling material represented by formula (1) itself and an inorganic filler surface-treated with the silane coupling material represented by formula (1). The dental curable composition of the present invention may not contain the silane coupling material represented by formula (1) itself, but may contain an inorganic filler surface-treated with the silane coupling material represented by formula (1). The dental curable composition of the present invention may not contain an inorganic filler surface-treated with the silane coupling material represented by formula (1), but may contain the silane coupling material represented by formula (1) itself.

[0040] In the present invention, when the dental curable composition contains the silane coupling material represented by formula (1), the composition ratio of the silane coupling material represented by formula (1) can be 0.05 to 5.0% by weight of the total dental curable composition if the dental curable composition does not contain a polymerization initiator, and 0.05 to 5.0% by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition contains a polymerization initiator. In other words, if the dental curable composition does not contain a polymerization initiator, the ratio can be 0.05 to 5.0 parts by weight per 100 parts by weight of the total dental curable composition, and if the dental curable composition contains a polymerization initiator, the ratio can be 0.05 to 5.0 parts by weight per 100 parts by weight of the dental curable composition excluding the polymerization initiator. If the content is lower than 0.05% by weight, the silane coupling material may not be sufficiently introduced. If it exceeds 5.0% by weight, a condensate of only the silane coupling material may be formed, which may affect the mechanical strength of the cured product.

[0041] In the present invention, when a dental curable composition contains an inorganic filler surface-treated with a silane coupling agent represented by formula (1), the treatment concentration in the surface treatment of the inorganic filler using the silane coupling agent represented by formula (1) can be 0.1 to 20% by weight of the inorganic filler. In other words, the amount of silane coupling agent treated per 100 parts by weight of the inorganic filler in the surface treatment can be 0.1 to 20 parts by weight. If the treatment amount is lower than 0.1% by weight, the silane coupling agent may not be sufficiently introduced. If it exceeds 20% by weight, a condensate of only the silane coupling agent may be formed, which may affect the mechanical strength of the cured product.

[0042] [Inorganic fillers] The inorganic fillers that can be used in the present invention are not particularly limited, but include silicon dioxide, alumina, silica-titania, silica-zirconia, silica-alumina, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, and the like. The dental curable composition of the present invention may contain these inorganic fillers after surface treatment with the silane coupling material represented by formula (1). The dental curable composition of the present invention may contain these inorganic fillers before surface treatment with the silane coupling material represented by formula (1). If the dental curable composition of the present invention contains the silane coupling material represented by formula (1) itself, it may contain only inorganic fillers that have not been surface-treated with the silane coupling material represented by formula (1) as the inorganic filler.

[0043] When the dental curable composition of the present invention contains the silane coupling material represented by formula (1) itself, the composition ratio of the inorganic filler before surface treatment with the silane coupling material represented by formula (1) in the dental curable composition of the present invention is not particularly limited, but if the dental curable composition does not contain a polymerization initiator, it can be 0.95 to 85% by weight of the entire dental curable composition, and can be 50 to 85% by weight. If the dental curable composition contains a polymerization initiator, it can be 0.95 to 85% by weight of the dental curable composition excluding the polymerization initiator, and can be 50 to 85% by weight. That is, if the dental curable composition does not contain a polymerization initiator, it can be 0.95 to 85 parts by weight of the inorganic filler per 100 parts by weight of the entire dental curable composition, and can be 50 to 85 parts by weight. If the content is lower than 0.95% by weight, the mechanical strength of the cured product may be low. Conversely, if the content is higher than 85% by weight, the viscosity of the prepared paste may be too high, resulting in poor workability.

[0044] The composition ratio of the inorganic filler after surface treatment with the silane coupling material represented by formula (1) in the dental curable composition of the present invention is not particularly limited, but if the dental curable composition does not contain a polymerization initiator, it can be 1 to 90% by weight of the total dental curable composition, or 70 to 85% by weight, and if the dental curable composition contains a polymerization initiator, it can be 1 to 90% by weight of the dental curable composition excluding the polymerization initiator, or 70 to 85% by weight. That is, if the dental curable composition does not contain a polymerization initiator, it can be 1 to 90 parts by weight of the silane coupling material excluding the polymerization initiator, or 70 to 85 parts by weight, per 100 parts by weight of the total dental curable composition, and if the dental curable composition contains a polymerization initiator, it can be 1 to 90 parts by weight of the silane coupling material excluding the polymerization initiator, or 70 to 85 parts by weight, per 100 parts by weight of the dental curable composition excluding the polymerization initiator. If the content is lower than 1% by weight, the mechanical strength of the cured product may be low. Also, if the content is higher than 90% by weight, the viscosity of the prepared paste may be too high, resulting in poor workability. When the dental curable composition of the present invention contains both the silane coupling material represented by formula (1) itself and an inorganic filler surface-treated with the silane coupling material represented by formula (1), the composition ratio after surface treatment with the silane coupling material represented by formula (1) refers to the composition ratio after surface treatment with the silane coupling material represented by formula (1) itself contained in the dental curable composition. That is, it refers to the total composition ratio of the inorganic filler and other surface-treated material that has been surface-treated with the silane coupling material represented by formula (1) itself contained in the dental curable composition, and the inorganic filler and other surface-treated material that has already been surface-treated with the silane coupling material represented by formula (1) before mixing with the silane coupling material represented by formula (1) itself.

[0045] The inorganic fillers used in this invention can be spherical or amorphous. Spherical inorganic fillers are those in which particles observed when photographed with an electron microscope are rounded or have no corners. Being spherical provides a sliding effect and is expected to reduce interference between fillers. Amorphous inorganic fillers are amorphous particles obtained by mechanical grinding. Amorphous particles can have any shape with corners. Being amorphous is expected to suppress fluidity and maintain the moldability of the paste. In the dental curable composition of this invention, spherical fillers and amorphous fillers can be used in combination from the viewpoint of achieving both fluidity and moldability of the paste. Furthermore, two or more types of fillers with different shapes and / or average particle sizes can be mixed or combined. By combining two or more types of fillers, the fillers are densely packed, and the number of interaction points between fillers and polymerizable monomers, or between fillers themselves, increases.

[0046] Furthermore, the average particle size of the inorganic filler used in the present invention can be 0.01 to 100 μm, 0.01 to 20 μm, or 0.01 to 10 μm. In addition, in the present invention, the average particle size of the inorganic filler surface-treated with the silane coupling material represented by formula (1) can be 0.01 to 100 μm, 0.01 to 20 μm, or 0.01 to 10 μm. If the average particle size of the inorganic filler is less than 0.01 μm, the dental hardening composition may become sticky, and the workability of the paste may deteriorate. On the other hand, if the average particle size of the inorganic filler exceeds 100 μm, it may lead to a decrease in the mechanical strength of the hardened product. By having the average particle size of the inorganic filler in the range of 0.01 to 10 μm, appropriate paste dispersibility can be obtained, and high mechanical strength after hardening can be achieved. In the present invention, the average particle size of the inorganic filler can be measured, for example, by a particle size analyzer, a laser diffraction particle size analyzer, or an electron microscope. Furthermore, the average particle size of the inorganic filler is not substantially affected by the surface treatment by the surface treatment agent. Therefore, the average particle size of the inorganic filler may be either in the state before surface treatment by the surface treatment agent or in the state after surface treatment by the surface treatment agent.

[0047] The shape of the inorganic filler is not particularly limited, but it can be spherical nanofiller. Being spherical provides excellent paste handling properties and allows for increased filling efficiency of dental curable compositions. Spherical nanofiller refers to nanoscale fillers whose particles, when photographed with an electron microscope, appear rounded. The spherical shape provides a sliding effect, reducing interference between fillers. The average particle diameter of spherical nanofillers can be 0.01-1 μm, 0.02-0.5 μm, or 0.05-0.1 μm. If the average particle diameter is less than 0.01 μm, the specific surface area increases, thickening the paste, which may prevent sufficient filler from being added, resulting in lower mechanical strength of the cured product. On the other hand, if the average particle diameter exceeds 1 μm, the surface area of ​​the spherical filler decreases, which may prevent the acquisition of a cured product of a dental curable composition with high formability. Note that the average particle diameter of spherical nanofillers is not substantially affected by surface treatment with surface treatment agents. Therefore, the average particle size of the spherical nanofillers may be either in the state before surface treatment with a surface treatment agent or in the state after surface treatment with a surface treatment agent.

[0048] The spherical nanofillers used in the present invention may be spherical nanofillers that have been hydrophobized with a surface treatment agent. The hydrophobization treatment may be performed before or after the surface treatment with the silane coupling material represented by formula (1). Furthermore, the hydrophobized spherical nanofillers may be those that have not been surface treated with the silane coupling material represented by formula (1). By including hydrophobized spherical nanofillers, in addition to the sliding effect that occurs when an external force is applied, the hydrophilic interaction that occurs between the polymerizable monomer and the filler is weakened, and the fluidity of the paste is not impaired when an external force is applied, thereby improving the fluidity of the paste.

[0049] The dental curable composition of the present invention may contain spherical nanofillers as an inorganic filler surface-treated with a silane coupling material represented by formula (1). The composition ratio of spherical nanofillers surface-treated with the silane coupling material represented by formula (1) in the dental curable composition of the present invention is not particularly limited, but if the dental curable composition does not contain a polymerization initiator, it can be 1 to 15% by weight of the total dental curable composition, and if the dental curable composition contains a polymerization initiator, it can be 1 to 15% by weight of the dental curable composition excluding the polymerization initiator, and can be 1 to 5% by weight. That is, if the dental curable composition does not contain a polymerization initiator, it can be 1 to 15 parts by weight per 100 parts by weight of the total dental curable composition, and if the dental curable composition contains a polymerization initiator, it can be 1 to 15 parts by weight per 100 parts by weight of the dental curable composition excluding the polymerization initiator, and can be 1 to 5 parts by weight. If the content is less than 1% by weight, the fluidity of the paste may be poor. Furthermore, if the content exceeds 15% by weight, the shapeability of the paste may be poor.

[0050] When the dental curable composition of the present invention contains the silane coupling material represented by formula (1) itself, the composition ratio of spherical nanofillers that are not surface-treated with the silane coupling material represented by formula (1) in the dental curable composition of the present invention is not particularly limited, but if the dental curable composition does not contain a polymerization initiator, it can be 1 to 14% by weight of the entire dental curable composition, or 1 to 5% by weight, and if the dental curable composition contains a polymerization initiator, it can be 1 to 14% by weight of the dental curable composition excluding the polymerization initiator, or 1 to 5% by weight. That is, if the dental curable composition does not contain a polymerization initiator, it can be 1 to 14 parts by weight of the dental curable composition excluding the polymerization initiator, or 1 to 5 parts by weight, and if the dental curable composition contains a polymerization initiator, it can be 1 to 14 parts by weight of the dental curable composition excluding the polymerization initiator, or 1 to 5 parts by weight, 1 to 14 parts by weight of the dental curable composition excluding the polymerization initiator, or 1 to 5 parts by weight. If it is less than 1% by weight, the fluidity of the paste may be poor. Furthermore, if the content exceeds 14% by weight, the shapeability of the paste may deteriorate.

[0051] Spherical nanofillers do not necessarily have to be manufactured or obtained as single particles; they may be obtained by mixing two or more spherical nanofillers with different average particle sizes and / or composition ratios, as long as their respective average particle sizes and composition ratios fall within the above range.

[0052] In particular, it is also effective to use spherical nanofillers that have been surface-treated with both a silane coupling material represented by formula (1) and a surface treatment agent other than the silane coupling material represented by formula (1).

[0053] The dental curable composition of the present invention may contain, in addition to an inorganic filler surface-treated with the silane coupling material represented by formula (1), spherical nanofillers not surface-treated with the silane coupling material represented by formula (1) as other fillers as described later. If the dental curable composition of the present invention does not contain the silane coupling material represented by formula (1) itself, it may contain, in addition to an inorganic filler surface-treated with the silane coupling material represented by formula (1), spherical nanofillers not surface-treated with the silane coupling material represented by formula (1) as other fillers as described later.

[0054] The shape of the inorganic filler is not particularly limited, but it can be a crushed inorganic filler. Being a crushed filler allows for shape-forming properties to be imparted to the paste. A crushed inorganic filler is an inorganic filler that has been mechanically crushed and can have any shape with arbitrary corners.

[0055] The average particle size of the crushed inorganic filler used in this invention can be 0.01 to 100 μm, and from the viewpoint of mechanical strength, it can be 0.01 to 20 μm, or 0.01 to 10 μm. If the average particle size is less than 0.01 μm, the specific surface area of ​​the crushed inorganic filler increases, which may reduce the fluidity of the paste. On the other hand, if the average particle size exceeds 100 μm, the dispersibility of the crushed inorganic filler in the dental curable composition deteriorates, which may prevent the production of a uniform paste.

[0056] The crushed inorganic filler used in the present invention may be a crushed inorganic filler that has been hydrophobized with a surface treatment agent. The hydrophobization treatment may be performed before or after the surface treatment with the silane coupling material represented by formula (1). Furthermore, the hydrophobized crushed inorganic filler may be one that has not been surface treated with the silane coupling material represented by formula (1). By including the hydrophobized crushed inorganic filler, the formability of the paste can be improved, and the mechanical strength of the dental hardened composition after hardening can be improved.

[0057] The dental curable composition of the present invention may include a crushed inorganic filler as an inorganic filler surface-treated with a silane coupling agent represented by formula (1). The composition ratio of the crushed inorganic filler surface-treated with the silane coupling agent represented by formula (1) in the dental curable composition of the present invention is not particularly limited, but if the dental curable composition does not contain a polymerization initiator, it can be 10 to 60% by weight of the total dental curable composition, or 20 to 50% by weight, and if the dental curable composition contains a polymerization initiator, it can be 10 to 60% by weight of the dental curable composition excluding the polymerization initiator, or 20 to 50% by weight. In other words, if the dental curable composition does not contain a polymerization initiator, the amount of polymerization initiator can be 10 to 60 parts by weight or 20 to 50 parts by weight per 100 parts by weight of the entire dental curable composition. If the dental curable composition contains a polymerization initiator, the amount of polymerization initiator can be 10 to 60 parts by weight or 20 to 50 parts by weight per 100 parts by weight of the dental curable composition excluding the polymerization initiator. If the amount is less than 10% by weight, the mechanical strength of the cured product may be low. Also, if the content exceeds 60% by weight, the viscosity of the prepared paste may be too high, resulting in poor workability.

[0058] When the dental curable composition of the present invention contains the silane coupling material represented by formula (1) itself, the composition ratio of the crushed inorganic filler that is not surface-treated with the silane coupling material represented by formula (1) in the dental curable composition of the present invention is not particularly limited, but if the dental curable composition does not contain a polymerization initiator, it can be 10 to 50% by weight of the entire dental curable composition, or 20 to 40% by weight, and if the dental curable composition contains a polymerization initiator, it can be 10 to 50% by weight of the dental curable composition excluding the polymerization initiator, or 20 to 40% by weight. That is, if the dental curable composition does not contain a polymerization initiator, it can be 10 to 50 parts by weight of the dental curable composition excluding the polymerization initiator, or 20 to 40 parts by weight, per 100 parts by weight of the entire dental curable composition, and if the dental curable composition contains a polymerization initiator, it can be 10 to 50 parts by weight of the dental curable composition excluding the polymerization initiator, or 20 to 40 parts by weight, per 100 parts by weight of the dental curable composition excluding the polymerization initiator. If the content is less than 10% by weight, the mechanical strength of the cured product may be low. Furthermore, if the content exceeds 50% by weight, the viscosity of the paste may be too high, resulting in poor workability.

[0059] Crushed inorganic fillers do not necessarily have to be manufactured or obtained as single particles; they may be obtained by mixing two or more crushed inorganic fillers with different average particle sizes and / or composition ratios, as long as their respective average particle sizes and composition ratios fall within the above range.

[0060] In particular, it is also effective to use in combination a silane coupling material represented by formula (1) and a crushed inorganic filler that has been surface-treated with a surface treatment agent other than the silane coupling material represented by formula (1).

[0061] The inclusion of crushed inorganic fillers results in superior mechanical strength of the cured product and excellent shapeability of the paste. Furthermore, combining crushed inorganic fillers with spherical nanofillers provides excellent fluidity for the paste of the dental curable composition of the present invention. In pastes with a high filling rate of inorganic fillers, for example, if a large amount of crushed inorganic fillers is used, the crushed inorganic fillers will catch on each other and interfere with each other when force is applied to the paste, increasing the viscosity of the paste and impairing its fluidity.

[0062] The dental curable composition of the present invention may contain, in addition to an inorganic filler surface-treated with the silane coupling material represented by formula (1), a crushed inorganic filler not surface-treated with the silane coupling material represented by formula (1) as another filler as described later. If the dental curable composition of the present invention does not contain the silane coupling material represented by formula (1) itself, it may contain, in addition to an inorganic filler surface-treated with the silane coupling material represented by formula (1), a crushed inorganic filler not surface-treated with the silane coupling material represented by formula (1) as another filler as described later.

[0063] The shape of the inorganic filler is not particularly limited, but it can be an aggregated inorganic filler. When the inorganic filler is an aggregate, the average particle diameter described later is the average particle diameter of the aggregate. An aggregated inorganic filler is a filler that has been granulated by a granulation process such as spray drying from nanoscale inorganic fillers. The cohesive force between the granulated fillers is expected to improve the mechanical strength of the dental hardening composition after curing.

[0064] The average particle size of the aggregated inorganic filler used in this invention can be 0.01 to 100 μm, and from the viewpoint of mechanical strength, it can be 0.01 to 20 μm, or 0.01 to 10 μm. If the average particle size is less than 0.01 μm, the specific surface area of ​​the aggregated inorganic filler increases, which may reduce the fluidity of the paste. On the other hand, if the average particle size exceeds 100 μm, the dispersibility of the aggregated inorganic filler in the dental curable composition deteriorates, which may prevent the production of a uniform paste.

[0065] The aggregated inorganic filler used in the present invention may be an aggregated inorganic filler that has been hydrophobized with a surface treatment agent. The hydrophobization treatment may be performed before or after the surface treatment with the silane coupling material represented by formula (1). Furthermore, the hydrophobized aggregated inorganic filler may be one that has not been surface treated with the silane coupling material represented by formula (1). By including a hydrophobized aggregated inorganic filler, the formability can be improved, and the mechanical strength of the dental hardened composition after hardening can be enhanced.

[0066] The dental curable composition of the present invention may include an aggregated inorganic filler as an inorganic filler surface-treated with a silane coupling agent represented by formula (1). The composition ratio of the aggregated inorganic filler surface-treated with the silane coupling agent represented by formula (1) in the dental curable composition of the present invention is not particularly limited, but if the dental curable composition does not contain a polymerization initiator, it can be 10 to 60% by weight of the total dental curable composition, or 20 to 50% by weight, and if the dental curable composition contains a polymerization initiator, it can be 10 to 60% by weight of the dental curable composition excluding the polymerization initiator, or 20 to 50% by weight. That is, if the dental curable composition does not contain a polymerization initiator, it can be 10 to 60 parts by weight of the dental curable composition excluding the polymerization initiator, or 20 to 50 parts by weight, per 100 parts by weight of the total dental curable composition, and if the dental curable composition contains a polymerization initiator, it can be 10 to 60 parts by weight of the dental curable composition excluding the polymerization initiator, or 20 to 50 parts by weight, per 100 parts by weight of the dental curable composition excluding the polymerization initiator. If the content is less than 10% by weight, the mechanical strength of the cured product may be low. Furthermore, if the content exceeds 60% by weight, the viscosity of the prepared paste may be too high, resulting in poor workability.

[0067] The aggregated inorganic filler in this invention is a zirconium silicate composed of "SiO2 / ZrO2". While the composition ratio is not particularly limited, it can be "SiO2 / ZrO2 = 50 / 50 to 99 / 1" or "SiO2 / ZrO2 = 70 / 30 to 90 / 10". If the ZrO2 content is 1 or less, the mechanical strength of the cured product may be low. If it is 50 or more, transparency of the dental curable composition may not be obtained.

[0068] When the dental curable composition of the present invention contains the silane coupling material represented by formula (1) itself, the composition ratio of the aggregated inorganic filler that is not surface-treated with the silane coupling material represented by formula (1) in the dental curable composition of the present invention is not particularly limited, but if the dental curable composition does not contain a polymerization initiator, it can be 9 to 55% by weight of the entire dental curable composition, or 19 to 47% by weight, and if the dental curable composition contains a polymerization initiator, it can be 9 to 55% by weight of the dental curable composition excluding the polymerization initiator, or 19 to 47% by weight. That is, if the dental curable composition does not contain a polymerization initiator, it can be 9 to 55 parts by weight of the dental curable composition excluding the polymerization initiator, or 19 to 47 parts by weight, per 100 parts by weight of the entire dental curable composition, and if the dental curable composition contains a polymerization initiator, it can be 9 to 55 parts by weight of the dental curable composition excluding the polymerization initiator, or 19 to 47 parts by weight, per 100 parts by weight of the dental curable composition excluding the polymerization initiator. If it is less than 9% by weight, the mechanical strength of the cured product may be low. Furthermore, if the content exceeds 55% by weight, the paste may become too viscous, resulting in poor handling.

[0069] Aggregated inorganic fillers do not necessarily have to be manufactured or obtained as single particles; they may be obtained by mixing two or more inorganic fillers with different average particle sizes and / or components, as long as their respective average particle sizes and composition ratios fall within the above range.

[0070] In particular, it is also effective to use in combination a silane coupling material represented by formula (1) and an aggregated inorganic filler surface-treated with a surface treatment agent other than the silane coupling material represented by formula (1).

[0071] By including aggregated inorganic fillers, the cured product can have excellent mechanical strength and excellent shapeability of the paste. Furthermore, by combining aggregated inorganic fillers with spherical nanofillers, the paste of the dental curable composition of the present invention can also be obtained to have excellent fluidity. In pastes with a high filling rate of inorganic fillers, for example, if a large amount of aggregated inorganic fillers is used, when force is applied to the paste, the aggregated inorganic fillers may catch on each other and interfere with each other, which can increase the viscosity of the paste and impair its fluidity.

[0072] The dental curable composition of the present invention may contain, in addition to an inorganic filler surface-treated with the silane coupling material represented by formula (1), an aggregated inorganic filler not surface-treated with the silane coupling material represented by formula (1) as another filler as described later. If the dental curable composition of the present invention does not contain the silane coupling material represented by formula (1) itself, it may contain, in addition to an inorganic filler surface-treated with the silane coupling material represented by formula (1), an aggregated inorganic filler not surface-treated with the silane coupling material represented by formula (1) as another filler as described later.

[0073] [Other fillers] The dental hardening composition of the present invention may optionally contain other known fillers other than inorganic fillers surface-treated with a silane coupling agent represented by formula (1). Other fillers used in the present invention include the above-mentioned inorganic filler that has not been surface-treated, the above-mentioned inorganic filler that has not been surface-treated with a silane coupling agent represented by the chemical structural formula of formula (1), the above-mentioned inorganic filler that has been surface-treated with a surface treatment agent other than the silane coupling agent represented by formula (1), organic fillers, organic-inorganic composite fillers, and the like.

[0074] If the dental curable composition contains the silane coupling material represented by formula (1), other fillers can be added to the dental curable composition after the surface treatment with the silane coupling material represented by formula (1) is completed.

[0075] Inorganic fillers surface-treated with surface treatment agents other than the silane coupling agent represented by formula (1) can be made into inorganic fillers surface-treated only with surface treatment agents other than the silane coupling agent represented by formula (1). Examples of such surface treatments include surface treatment with 3-methacryloxypropyltrimethoxysilane, surface treatment with 8-methacryloxyoctyltrimethoxysilane, and surface treatment with titanium acetylacetonate. By using two or more surface treatment agents, including a surface treatment agent other than the silane coupling agent represented by formula (1), it becomes possible to freely adjust the polymerizability of the polymerizable monomer, the dispersibility of the filler, the paste handling properties and shapeability, the paste stability, and the mechanical strength after curing of the dental curable composition as a whole.

[0076] Inorganic fillers surface-treated with surface treatment agents other than the silane coupling agent represented by formula (1) can be present in amounts of 1 to 50% by weight of the total dental curable composition if the dental curable composition does not contain a polymerization initiator, and can be present in amounts of 10 to 40% by weight. That is, they can be present in amounts of 1 to 50 parts by weight, and can be present in amounts of 10 to 40 parts by weight, per 100 parts by weight of the total dental curable composition. If the amount is less than 1% by weight, the workability of the paste may be poor, and if it exceeds 50% by weight, the mechanical strength after curing may decrease. Furthermore, if the dental curable composition contains a polymerization initiator, the amount can be present in amounts of 20 to 40% by weight of the dental curable composition excluding the polymerization initiator. That is, they can be present in amounts of 20 to 40% by weight of the dental curable composition excluding the polymerization initiator, per 100 parts by weight of the dental curable composition excluding the polymerization initiator. If the amount is less than 20% by weight, the workability of the paste may be poor, and if it exceeds 40% by weight, the mechanical strength after curing may decrease.

[0077] Examples of organic fillers include, but are not limited to, polyvinyl acetate, polyvinyl alcohol, elastomers such as styrene-butadiene rubber, non-crosslinked (meth)acrylate polymers which are homopolymers of monofunctional (meth)acrylate polymerizable monomers such as polymethyl methacrylate (PMMA), polyethyl methacrylate, polypropyl methacrylate, and polybutyl methacrylate, crosslinked (meth)acrylate polymers obtained by copolymerizing a monofunctional (meth)acrylate polymerizable monomer with a polymerizable monomer having two or more functional groups, polyvinyl acetate, polyethylene glycol, polypropylene glycol, and polyvinyl alcohol.

[0078] Examples of organic-inorganic composite fillers include, but are not limited to, those in which the surface of the filler is polymerized and coated with a polymerizable monomer, those in which the filler and polymerizable monomer are mixed and polymerized and then pulverized to an appropriate particle size, or those in which the filler is dispersed in a polymerizable monomer beforehand and subjected to emulsion polymerization or suspension polymerization.

[0079] These organic fillers and organic-inorganic composite fillers may or may not be surface-treated.

[0080] The dental hardening composition of the present invention may be free from inorganic fillers that have not been surface-treated with a silane coupling agent represented by formula (1). The dental hardening composition of the present invention may be free from fillers other than inorganic fillers that have been surface-treated with a silane coupling agent represented by formula (1). The dental hardening composition of the present invention may be free from inorganic fillers that have not been surface-treated. The dental hardening composition of the present invention may be free from fillers that have not been surface-treated.

[0081] [Radical polymerizable monomers] The amount of radical polymerizable monomer to be incorporated into a specific dental curable composition containing the inorganic filler of the present invention can be 10 to 60% by weight of the total dental curable composition if the dental curable composition does not contain a polymerization initiator, or 15 to 30% by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition does contain a polymerization initiator. That is, if the dental curable composition does not contain a polymerization initiator, the amount can be 10 to 60 parts by weight of the total dental curable composition per 100 parts by weight, or 15 to 30 parts by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition does contain a polymerization initiator. If the amount is less than 10% by weight, the viscosity of the dental curable composition may be too high, potentially impairing the operability of the paste, and if it exceeds 60% by weight, the mechanical strength of the cured product of the dental curable composition may decrease.

[0082] The radical polymerizable monomers used in the dental curable composition of the present invention can be any monomer used in the dental field without limitation, but they may have urethane bonds or hydrogen bonds in their molecular skeleton. This is to effectively form hydrogen bonds with the silane coupling material used in the present invention. Examples of monomers that do not contain urethane bonds or hydrogen bonds include phenoxyethyl acrylate, methyl methacrylate, tetrahydrofurfuryl acrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, and bisphenol A diethoxylate diacrylate.

[0083] The number of functional groups in the radical polymerizable monomer used in this invention can be 2 to 9. In the case of monofunctional monomers, a crosslinking structure may not be formed, and the dental hardening composition may not be able to be given sufficient mechanical strength. On the other hand, in the case of 10 or more functional monomers, the density of the crosslinking structure may become too high, which may lead to fragility in the dental hardening composition. In this invention, the functionality of the radical polymerizable monomer refers to the number of polymerizable groups such as (meth)acryloyl groups.

[0084] The radical polymerizable monomer may have a urethane bond. Specifically, the amount of radical polymerizable monomer containing a urethane bond can be 10 to 50% by weight of the total dental curable composition if the dental curable composition does not contain a polymerization initiator, or 15 to 30% by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition does contain a polymerization initiator. In other words, if the dental curable composition does not contain a polymerization initiator, it can be 10 to 50 parts by weight of the radical polymerizable monomer per 100 parts by weight of the total dental curable composition, or 15 to 30 parts by weight of the radical polymerizable monomer per 100 parts by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition does contain a polymerization initiator. If the amount is less than 10% by weight, the mechanical strength of the cured product of the dental curable composition may decrease. If the urethane content exceeds 50% by weight, the viscosity of the dental curable composition may become too high, potentially impairing the handling of the paste. In this invention, a urethane bond refers to a bond having an -NH-C(=O)-O- group. Examples of such radical polymerizable monomers include di(meth)acrylates having bifunctional or more urethane bonds derived from adducts of polymerizable monomers having hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-chloro-2-hydroxypropyl (meth)acrylate, with diisocyanate compounds such as methylcyclohexane diisocyanate, methylenebis(4-cyclohexyl isocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylmethylbenzene, and 4,4-diphenylmethane diisocyanate.

[0085] Radical polymerizable monomers may have hydrogen bonds. Specifically, the amount of radical polymerizable monomers containing hydrogen bonds can be 1 to 20% by weight of the total dental curable composition if the dental curable composition does not contain a polymerization initiator, or 1 to 10% by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition does contain a polymerization initiator. That is, if the dental curable composition does not contain a polymerization initiator, it can be 1 to 20 parts by weight of the total dental curable composition per 100 parts by weight, or 1 to 10 parts by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition does contain a polymerization initiator, it can be 1 to 20 parts by weight of the dental curable composition excluding the polymerization initiator, or 1 to 10 parts by weight of the dental curable composition excluding the polymerization initiator. If it is less than 1% by weight, the viscosity of the dental curable composition may be too high, which may impair the workability of the paste. If it exceeds 20% by weight, the mechanical strength of the cured product of the dental curable composition may decrease. Examples of such radically polymerizable monomers include 2-hydroxy-1,3-dimethacryloxypropane, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, and 2-acryloyloxyethylhexahydrophthalic acid.

[0086] Radical polymerizable monomers can be monomers having one or more hydroxyl groups and two or more polymerizable groups. In the present invention, two or more polymerizable groups refer to the number of polymerizable groups such as two or more (meth)acryloyl groups. Examples of such radical polymerizable monomers include 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-1,3-diacroxypropane, 2-hydroxy-3-acryloyloxypropyl methacrylate, and 2-acryloyloxyethyl monomethyltetrahydrophthalate. Having one or more hydroxyl groups and two or more polymerizable groups allows for appropriate paste dispersibility and high mechanical strength after curing.

[0087] As a radical polymerizable monomer having one or more hydroxyl groups and two or more polymerizable groups, the monomer represented by formula (2) can be used. The monomer represented by formula (2) can be used in an amount of 1 to 20% by weight of the total dental curable composition if the dental curable composition does not contain a polymerization initiator, and in an amount of 1 to 20% by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition contains a polymerization initiator. That is, if the dental curable composition does not contain a polymerization initiator, the monomer can be used in an amount of 1 to 20 parts by weight per 100 parts by weight of the total dental curable composition, and in an amount of 1 to 20 parts by weight per 100 parts by weight of the dental curable composition excluding the polymerization initiator if the dental curable composition contains a polymerization initiator. If the content is less than 1% by weight, the viscosity of the dental curing composition may be too high, impairing the workability of the paste. If it is more than 20% by weight, the mechanical strength of the dental curing composition may decrease. The optimal content allows for the formation of hydrogen bonds with the amide bonds contained in the silane coupling agent, improving the mechanical strength of the cured product. [Formula (2)] [ka]

[0088] When the dental curable composition of the present invention contains the silane coupling material represented by formula (1) itself, the weight ratio of the silane coupling material represented by formula (1) to the radical polymerizable monomer having the compound represented by formula (2) can be in the range of 1:0.5 to 1:20. If the weight ratio of the radical polymerizable monomer having the compound represented by formula (2) to the silane coupling material represented by formula (1) is less than 1:0.5, the viscosity of the dental curable composition may be too high, impairing the workability of the paste, and if it exceeds 1:20, the mechanical strength of the dental curable composition may decrease.

[0089] [Polymerization initiator] The polymerization initiator used in the present invention is not particularly limited, and any known radical-generating material can be used without any restrictions. Polymerization initiators are generally broadly classified into those that initiate polymerization by heating (thermal polymerization initiators), those that initiate polymerization by light irradiation (photopolymerization initiators), and those that initiate polymerization by mixing two forms of composition (chemical polymerization initiators). In the present invention, thermal polymerization initiators are preferably used as polymerization initiators from the viewpoint of mechanical strength after curing.

[0090] Organic peroxides can be preferably used as thermal polymerization initiators. Specific examples include benzoyl peroxide, parachlorobenzoyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tert-butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, and tert-butyl peroxybenzoate.

[0091] The thermal polymerization initiator in this invention can be selected from, for example, thermal polymerization initiators used in general industry that have a specific 10-hour half-life temperature.

[0092] In this invention, the 10-hour half-life temperature of the thermal polymerization initiator is 50 to 200°C, and can be 90 to 170°C from the viewpoint of mechanical strength. By setting an appropriate 10-hour half-life temperature range, the polymerization rate can be improved even when using high-viscosity radical polymerizable monomers, and the mechanical strength of the resulting cured product is improved. If the 10-hour half-life temperature is lower than 50°C, a sufficient polymerization rate may not be obtained when using high-viscosity polymerizable monomers, and the mechanical strength may decrease. If it is higher than 200°C, thermal degradation may cause a decrease in the mechanical strength and yellowing of the cured product. In this invention, the 10-hour half-life temperature refers to the temperature at which the half-life of the thermal polymerization initiator is 10 hours, and the half-life refers to the time it takes for the concentration of the thermal polymerization initiator to decrease to half of its initial value. Examples of thermal polymerization initiators with a 10-hour half-life temperature between 70°C and 170°C include 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis[4,4-bis(isobutylperoxy)cyclohexyl]propane, tert-butylperoxyisopropyl carbonate, tert-butyl dodecaneperoxyate, tert-butyloxy(2-ethylhexyl) carbonate, bis(1-phenyl-1-methylethyl)peroxide, di-tert-butylperoxide, and 2,5-dimethyl-2,5-di-(tert-butylperoxyl)-hexyne-3.

[0093] Examples of photopolymerization initiators include α-diketones such as camphorquinone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, acetonafthene, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and naphthoquinone; benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, and 2,4-diethylthioxanthone.

[0094] Examples of chemical polymerization initiators include redox-type polymerization catalyst systems consisting of organic peroxide / amine compounds or organic peroxide / amine compounds / sulfinates, and organic peroxide / amine compounds / borates; and polymerization catalyst systems such as organoboron compounds, perborates, permanganates, and persulfates that initiate polymerization by reacting with oxygen and water. Furthermore, sulfinates, borate compounds, and barbiturates can also initiate polymerization by coexisting with water and / or polymerizable monomers having acidic groups.

[0095] Examples of organic peroxides include, but are not limited to, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tert-butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, and tert-butyl peroxybenzoate. Furthermore, these organic peroxides can be used individually or in combination.

[0096] Preferred amine compounds are secondary or tertiary amines in which an amine group is bonded to an aryl group. Specific examples include, but are not limited to, N,N-dimethyl-p-toluidine, N,N-dimethylaniline, N-β-hydroxyethyl-aniline, N,N-di(β-hydroxyethyl)-aniline, N,N-di(β-hydroxyethyl)-p-toluidine, N-methyl-aniline, and N-methyl-p-toluidine. Furthermore, these amine compounds can be used individually or in combination.

[0097] Examples of sulfinate salts include sodium benzenesulfinate and ben Examples include lithium benzosulfinate and sodium p-toluenesulfinate, but are not limited to these. Furthermore, the above sulfinates can be used individually or in combination.

[0098] Examples of borate compounds include, but are not limited to, the sodium, lithium, potassium, magnesium, tetrabutylammonium, and tetramethylammonium salts of trialkylphenylboron and trialkyl(p-fluorophenyl)boron (with alkyl groups such as n-butyl, n-octyl, and n-dodecyl groups). Furthermore, these borate compounds can be used individually or in combination. Specific examples of barbiturates include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5- Examples include, but are not limited to, ethyl barbituric acid, 1-benzyl-5-phenylbarbituric acid, and thiobarbituric acids, as well as their salts (particularly alkali metals or alkaline earth metals), such as sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, calcium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate. Furthermore, the above barbituric acids can be used individually or in combination.

[0099] Among these chemical polymerization initiators, a combination of organic peroxide and tertiary amine can be used.

[0100] These polymerization initiators can be used individually or in combination of two or more, regardless of the polymerization mode or method. Furthermore, these polymerization initiators can be subjected to secondary treatments, such as encapsulation in microcapsules, as needed, without any problems. The dental curable composition of the present invention may contain only a thermal polymerization initiator. The dental curable composition of the present invention may contain only a photopolymerization initiator.

[0101] The content of the polymerization initiator used in this invention can be appropriately selected depending on the application, but it can be in the range of 0.01 to 10 parts by weight, or 0.1 to 5 parts by weight, per 100 parts by weight of radical polymerizable monomer. If there is too much polymerization initiator, cracking is likely to occur when manufacturing the hardened resin for dental cutting, which can make manufacturing difficult. If there is too little polymerization initiator, sufficient effect cannot be obtained, and the mechanical strength will decrease.

[0102] The dental curable composition of the present invention may contain various known additives as needed. Examples of additives used in the present invention include polymerization inhibitors, chain transfer agents, colorants, discoloration inhibitors, fluorescent agents, ultraviolet absorbers, and antibacterial agents. The dental curable composition of the present invention may contain only one or more additives selected from polymerization inhibitors, chain transfer agents, colorants, discoloration inhibitors, fluorescent agents, ultraviolet absorbers, and antibacterial agents.

[0103] The dental curable composition of the present invention can achieve a flexural strength of 300 MPa or more after storage in water at 37°C for one week in the cured body. This flexural strength of 300 MPa or more provides a dental curable composition with excellent processability to complex shapes and superior durability. The flexural strength can be measured using a universal testing machine (manufactured by Instron) in accordance with ISO 6872, at a crosshead speed of 1 mm / min.

[0104] The dental curable composition of the present invention can have a flexural modulus of 20 GPa or more after storage in water at 37°C for one week in the cured body. Having a flexural modulus of 20 GPa or more provides a dental curable composition with excellent processability to complex shapes and durability. The flexural modulus can be measured using a universal testing machine (manufactured by Instron) in accordance with ISO 6872, at a crosshead speed of 1 mm / min.

[0105] The dental curing composition of the present invention can be used, for example, in the manufacture of dental cutting resin curing bodies, in the manufacture of dental composite resins, and in dental curing compositions for 3D printers. [Examples]

[0106] The following describes specific examples of the present invention, but the present invention is not limited to these examples. The abbreviations, physical properties, and test methods of each component in the examples and comparative examples are as follows.

[0107] [Inorganic filler] ZSF: Agglomerated zirconium silicate (d 50 :2μm) GM32087: Fragmented strontium almobolosilicate glass (d 50 (0.4 μm, manufactured by SCHOTT) Aerosil R-7200: Irregularly shaped amorphous silica (Primary particle size: 12 nm, manufactured by Nippon Aerosil Co., Ltd.) Aerosil OX-50: Irregularly shaped amorphous silica (Primary particle size: 40 nm, manufactured by Nippon Aerosil Co., Ltd.) Admanano YC100C-SM2: Spherical amorphous silica (Primary particle size: 100 nm, manufactured by Admatex Co., Ltd.)

[0108] [Surface treatment agent] <Silane coupling material represented by formula (1)> X-12-1370: N-(3-trimethoxysilyl)propyl)methacrylamide (molecular weight 247, manufactured by Shin-Etsu Chemical Co., Ltd.) <Silane coupling materials other than those represented by formula (1)> KBM-503: 3-Methacryloxypropyltrimethoxysilane (Molecular weight 248, manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-502: 3-Methacryloxypropylmethyldimethoxysilane (Molecular weight 232, manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-5803: 8-Methacryloxyoctyltrimethoxysilane (Molecular weight 319, manufactured by Shin-Etsu Chemical Co., Ltd.) TC-100: Titanium acetylacetonate (manufactured by Matsumoto Fine Chemical Co., Ltd.) TC-401: Titanium tetraacetylacetonate (manufactured by Matsumoto Fine Chemical Co., Ltd.) TC-750: Titanium ethyl acetoacetate (manufactured by Matsumoto Fine Chemical Co., Ltd.) ZC-200: Zirconium octylate compound (manufactured by Matsumoto Fine Chemical Co., Ltd.) ZC-580: Zirconium ethyl acetate (manufactured by Matsumoto Fine Chemical Co., Ltd.) KBE-9103P: 3-[(1,3-dimethylbutylidene)amino]propyltriethoxysilane (molecular weight 304, manufactured by Shin-Etsu Chemical Co., Ltd.) X-12-1135: Organosiloxane containing a carboxyl group (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0109] [Radical polymerizable monomers] <Radical polymerizable monomers containing urethane bonds> GENOMER 4267: Aliphatic urethane acrylate (viscosity 16,000 mPas @ 60℃, Rahn) GENOMER 4247: Aliphatic urethane methacrylate (viscosity 10,000 mPas @ 25℃, Rahn) GENOMER 4425: Aliphatic urethane acrylate (viscosity 4,500 mPas @ 25℃, Rahn) <Radical polymerizable monomers containing hydrogen bonds> HEMA: 2-hydroxyethyl methacrylate (viscosity: 7 mPa·s (20℃), manufactured by Mitsubishi Chemical Corporation) M-600A: 2-Hydroxy-3-Phenoxypropyl Acrylate (Viscosity: 150 mPa·s (25℃), manufactured by Kyoeisha Chemical Co., Ltd.) <Polymerizable monomer having one or more hydroxyl groups and two or more polymerizable groups> G-201P: 2-Hydroxy-3-Acryloyloxypropyl Methacrylate (Viscosity: 50 mPa, manufactured by Kyoeisha Chemical Co., Ltd.) <Polymerizable monomer represented by formula (2)> NK Ester 701: 2-Hydroxy-1,3-Dimethacryloxypropane (Viscosity: 37 mPa·s (25℃), manufactured by Shin Nakamura Chemical Industry Co., Ltd.) <Other radical polymerizable monomers> 14EG: Polyethylene glycodimethacrylate (viscosity: 60 mPa·s (25℃), manufactured by Kyoeisha Chemical Co., Ltd.) BP-2EM: Bisphenol A EO adduct dimethacrylate (viscosity: 1400 mPa·s (25℃), manufactured by Kyoeisha Chemical Co., Ltd.) 3G: Triethylene glycol dimethacrylate (viscosity: 9 mPa·s (25℃), manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0110] [Polymerization initiator] <Thermal polymerization initiator> Perhexa C: 1,1-bis(tert-butylperoxy)cyclohexane (10-hour half-life temperature: 90.7°C, manufactured by NOF Corporation) Perhexa V: n-butyl=4,4-bis(tert-butylperoxy)valerate (10-hour half-life temperature: 104.5℃, manufactured by NOF Corporation) Perhexyl D: Di-t-hexyl peroxide (10-hour half-life temperature: 116.4°C, manufactured by NOF Corporation)

[0111] [others] γ-Terpinene: γ-Terpinene (Molecular weight: 136.4, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0112] (Preparation of various surface treatment inorganic fillers) Surface treatment was performed on 100g of untreated inorganic filler using the surface treatment agents in the combinations shown in Table 1. Specifically, 100g of untreated inorganic filler was mixed with a surface treatment solution (prepared by stirring the surface treatment agent in the proportions listed in Table 1, 6g of water, 6g of ethanol, and 0.1g of phosphoric acid), and stirred for 15 minutes. After that, heat treatment was carried out at 115°C for 3 hours to obtain the heat-treated product.

[0113] Processing volume of each inorganic filler

[0114] [Table 1]

[0115] (Preparation of hardened resin bodies for dental cutting) The amounts of each component used in each example and comparative example are shown in Tables 2 and 3. Each component shown in Tables 2 and 3 was kneaded and degassed under reduced pressure to obtain a mixture (dental curable composition). After filling the mixture into an aluminum mold, it was sandwiched between aluminum plates, subjected to vacuum pressure, and then cured by hot pressing under the conditions of "130°C-3.5t-5min". Subsequently, an additional heat treatment at 150°C for 8 hours was performed to obtain a dental cutting resin cured body used for mechanical strength testing.

[0116] (Method for measuring the mechanical strength of hardened dental cutting resin) Test specimens (19.0 × 4.0 × 1.2 mm) were cut from a hardened dental cutting resin and their surfaces were smoothed with waterproof abrasive paper (#2000). The prepared test specimens were immersed in deionized water and stored at 37°C for 7 days. Subsequently, the bending strength and bending modulus were measured using a universal testing machine (Instron 5967, manufactured by Instron) in accordance with ISO 6872 at a crosshead speed of 1 mm / min.

[0117] The test results of the prepared dental hardening compositions are shown in Tables 2 to 7.

[0118] [Table 2]

[0119] [Table 3]

[0120] [Table 4]

[0121] [Table 5]

[0122] [Table 6]

[0123] [Table 7]

[0124] [Examples 1-52] The dental curable compositions of Examples 1 to 52 were found to exhibit high flexural strength and flexural modulus, demonstrating excellent mechanical strength.

[0125] [Comparative Examples 1-22] The dental hardening compositions of Comparative Examples 1 to 22 were found to have lower mechanical strength because they did not contain inorganic fillers surface-treated with X-12-1370.

[0126] Thus, the dental curable composition prepared according to the present invention had significantly higher flexural strength compared to conventional dental curable compositions using silane coupling materials (such as KBM-503) (Comparative Examples 1-22). The present invention makes it possible to provide a dental curable composition that has high mechanical strength after curing, which could not be achieved with conventional techniques. [Industrial applicability]

[0127] According to the present invention, it is possible to provide a dental curable composition that can obtain high mechanical strength after curing.

Claims

1. A dental curable composition comprising a silane coupling agent represented by formula (1), and / or an inorganic filler surface-treated with a silane coupling agent represented by formula (1). [Formula (1)] 【Chemistry 1】

2. The dental curable composition according to claim 1, comprising an inorganic filler surface-treated with a silane coupling agent represented by formula (1).

3. A dental curable composition comprising an inorganic filler according to claim 2, wherein the amount of silane coupling material treated in the surface treatment is 0.1 to 20 parts by weight per 100 parts by weight of the inorganic filler.

4. The dental curable composition according to claim 2, wherein the amount of inorganic filler surface-treated with a silane coupling material represented by formula (1) is 1 to 90 parts by weight per 100 parts by weight of the entire dental curable composition.

5. The dental curable composition according to claim 1, further comprising a radical polymerizable monomer and a polymerization initiator.

6. The dental curable composition according to claim 5, further comprising an inorganic filler surface-treated with a surface treatment agent other than a silane coupling agent represented by formula (1).

7. The dental curable composition according to claim 5, wherein the radical polymerizable monomer has a urethane bond.

8. The dental curable composition according to claim 5, wherein the radical polymerizable monomer has one or more hydroxyl groups and two or more polymerizable groups.

9. The dental curable composition according to claim 8, comprising a monomer represented by formula (2) as a radical polymerizable monomer. [Formula (2)] 【Chemistry 2】

10. The dental curable composition according to claim 9, wherein the amount of radical polymerizable monomer having a compound represented by formula (2) is 1 to 10 parts by weight per 100 parts by weight of the entire dental curable composition.

11. The dental curable composition according to claim 9, wherein the weight ratio of a silane coupling material represented by formula (1) and a radical polymerizable monomer having a compound represented by formula (2) is in the range of 1:0.5 to 1:

20.

12. The dental curable composition according to claim 2, wherein the inorganic filler surface-treated with a silane coupling material represented by formula (1) is a spherical nanofiller having an average particle size of 0.01 to 1 μm.

13. The dental curable composition according to claim 2, wherein the inorganic filler surface-treated with a silane coupling material represented by formula (1) is a crushed inorganic filler having an average particle size of 0.01 to 10 μm.

14. The dental curable composition according to claim 2, wherein the inorganic filler surface-treated with a silane coupling material represented by formula (1) is an aggregated inorganic filler having an average particle size of 0.01 to 10 μm.

15. Aggregated inorganic filler is SiO ２ : 50-99% by weight and ZrO ２ A dental curable composition according to claim 14, comprising 1-50% by weight.

16. The dental curable composition according to claim 5, wherein the 10-hour half-life temperature of the polymerization initiator is between 70°C and 170°C.

17. The dental curable composition according to claim 5, wherein the cured body of the dental curable composition has a flexural strength of 300 MPa or more after being stored in water at 37°C for one week.

18. The dental curable composition according to claim 5, wherein the cured body of the dental curable composition has a flexural modulus of 20 GPa or more after being stored in water at 37°C for one week.

19. A dental curable composition according to claim 5, used in the manufacture of a dental cutting resin curing body.

20. A dental curable composition according to claim 5, used in the manufacture of dental composite resin.

21. The dental curable composition according to claim 5, used in dental curable compositions for 3D printers.

22. An inorganic filler surface-treated with a silane coupling material represented by formula (1). [Formula (1)] 【Transformation 3】

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