Dental curable composition

Abstract

To provide a dental curable composition that offers ion-releasing capability and exhibits excellent mechanical strength and bonding durability.SOLUTION: A dental curable composition comprises: (A) a polyalkylene di(meth)acrylate-based monomer, (B) a polymerization initiator, and (C) an ion-releasing compound, wherein the polyalkylene di(meth)acrylate-based monomer (A) is a compound represented by general formula [I] (where R1 is a hydrocarbon group having 2 to 4 carbon atoms, R2 and R3 are each independently hydrogen or a methyl group, and n is an integer from 4 to 12).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dental hardenable composition suitable for dental filling and restorative materials, dental cements, dental core building materials and dental adhesives. [Background technology]

[0002] Dental composite resins, which are mainly composed of polymerizable monomers, fillers, and polymerization initiators, are the most widely used dental materials today as materials for repairing missing teeth or cavities, and for bonding dental prostheses, such as dental filling and restorative materials, dental cements, and dental core construction materials. There is a demand for improvements in such dental composite resins in the following respects: For the cured product, the mechanical strength is improved and polymerization shrinkage during curing is reduced.

[0003] Secondary caries occurs when bacteria enter construction gaps that arise due to improper treatment, peeling of dental composite resin from its adhesive surface, or deterioration of the dental composite resin at the adhesive surface, and there is a strong desire to prevent this secondary caries as much as possible. Generally, a method for preventing secondary caries is to form an acid-resistant layer on the tooth structure to strengthen it. One method for strengthening tooth structure is to supply ions, including fluoride ions, to the tooth structure. Specifically, this can be achieved by mixing ion-releasing compounds into dental composite resins, or by using a material called glass ionomer, which is a mixture of inorganic compounds and polycarboxylic acids.

[0004] However, when an ion-releasing compound is mixed into a dental composite resin, not only is sufficient ion-releasing ability not obtained, but there are also problems with the strength and adhesive durability being impaired due to water absorption, etc. Also, although glass ionomers have excellent ion-releasing ability, they have problems with low strength and low adhesiveness. As examples of techniques for imparting such ion releasing properties and developing strength, Patent Documents 1 to 3 are given. Patent Document 1 describes an example of a dental composition in which a fluoride-releasing compound is encapsulated with polysiloxane. Patent Document 2 describes an example of a dental composition containing a polymerizable monomer containing an alkylene glycol skeleton of a specific chain length and a fluoride-releasing component. Patent Document 3 describes an example of a dental composition containing a (meth)acrylic monomer containing a urethane bond, a (meth)acrylic acid ester compound containing two or more (meth)acryloyloxy groups and one or more hydroxyl groups in one molecule, and an ion-releasing compound. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2006 / 106838 [Patent Document 2] Patent Publication No. 2002-145715 [Patent Document 3] International Publication No. 2023 / 120611 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the inventors have found that the dental ion-releasing composition described in Patent Document 1 has a low level of mechanical strength, although it can achieve a certain level of ion release. On the other hand, it is difficult to further improve the ion release of the dental hardenable compositions described in Patent Documents 2 and 3, and there is room for improvement in both mechanical strength and ion release. Moreover, Patent Documents 1 to 3 do not suggest ejection properties.

[0007] Therefore, an object of the present invention is to provide a dental curable composition which has high ion releasing properties, and is excellent in mechanical strength and adhesion durability. [Means for solving the problem]

[0008] That is, the present invention includes the following inventions. [1] A composition comprising a polyalkylene di(meth)acrylate monomer (A), a polymerization initiator (B) and an ion-releasing compound (C), The polyalkylene di(meth)acrylic acid ester monomer (A) is represented by the following general formula [I]: [ka] (In the formula, R 1 is a hydrocarbon group having 2 to 4 carbon atoms, and R 2 and R 3 are each independently a hydrogen atom or a methyl group, and n is an integer of 4 to 12. a dental hardenable composition, which is a compound represented by the formula: [2] The dental curable composition according to [1], further comprising a (meth)acrylic monomer (D) containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule; [3] The dental curable composition according to [1] or [2], further comprising a polymerizable monomer (E) other than the polyalkylene di(meth)acrylic acid ester monomer (A) and the (meth)acrylic monomer (D); [4] The dental curable composition according to any one of [1] to [3], further comprising a polymerization accelerator (F); [5] The dental curable composition according to any one of [1] to [4], further comprising a filler (G); [6] The dental curable composition according to any one of [1] to [5], wherein the ion-releasing compound (C) contains at least one selected from the group consisting of a fluoride ion-releasing compound and a calcium ion-releasing compound; [7] The dental curable composition according to any one of [2] to [6], wherein the (meth)acrylic monomer (D) does not contain a polymer skeleton; [8] The dental curable composition according to any one of [2] to [7], wherein the (meth)acrylic monomer (D) is a compound having a molecular weight of 1,000 or less; [9] The content of the polyalkylene di(meth)acrylic acid ester monomer (A) is 1 to 90 parts by mass in 100 parts by mass of the total amount of the polymerizable monomers; and The dental curable composition according to any one of [2] to [8], wherein the content of the (meth)acrylic monomer (D) is 20 to 95 parts by mass in 100 parts by mass of the total amount of the polymerizable monomers;

[10] The dental curable composition according to any one of [2] to [9], wherein the value represented by the content of the (meth)acrylic monomer (D) / the content of the polyalkylene di(meth)acrylic acid ester monomer (A) is 1 or more;

[11] A dental filling and restorative material comprising the dental hardenable composition according to any one of [1] to

[10] ;

[12] A dental cement comprising the dental hardenable composition according to any one of [1] to

[10] .

[13] A dental core build-up material comprising the dental hardenable composition according to any one of [1] to

[10] ;

[14] A dental adhesive comprising the dental curable composition according to any one of [1] to

[10] . Effect of the Invention

[0009] According to the present invention, it is possible to provide a dental curable composition having high ion releasing properties, and excellent mechanical strength and adhesion durability. In addition, the present invention can provide a dental curable composition having excellent ejection properties, which makes it easier to finely adjust the filling amount in an operation such as pushing out the dental curable composition from a syringe when filling a cavity in dental treatment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the present invention will be described in detail with reference to embodiments. In this specification, the upper and lower limit values ​​of the numerical ranges (contents of each component, values ​​calculated from each component, and each physical property, etc.) can be appropriately combined. In addition, in this specification, the numerical values ​​of each symbol in the formula can also be appropriately combined. In other words, in this specification, the lower limit and upper limit described in stages for numerical ranges can be combined independently. For example, the description of "preferably 10 to 90, more preferably 30 to 60" for the same item can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." Furthermore, with regard to a numerical range, for example, based on the description of "preferably 10 to 90, more preferably 30 to 60," the upper limit value can be not particularly specified and only the lower limit value can be specified as "10 or more" or "30 or more," and similarly, the lower limit value can be not particularly specified and only the upper limit value can be specified as "90 or less" or "60 or less." Unless otherwise specified, when a numerical range is simply stated as "10 to 90", it indicates a range of 10 or more and 90 or less. As above, for example, from the description of "preferably 10 or more, more preferably 30 or more" and the description of "preferably 90 or less, more preferably 60 or less" for the same item, the "preferable lower limit (10)" and the "more preferable upper limit (60)" can be combined to form "10 or more and 60 or less." Also, as above, only the lower limit can be specified as "10 or more" or "30 or more," and similarly, only the upper limit can be specified as "90 or less" or "60 or less." In this specification, the term "(meth)acrylic" is used to mean both "methacrylic" and "acrylic". The same applies to similar terms such as "(meth)acrylate", "(meth)acrylic acid ester", "(meth)acrylamide", and "(meth)acryloyloxy". In addition, in this specification, the term "(meth)acrylic monomer" or "(meth)acrylic compound" is used to mean both "(meth)acrylic acid ester compound" and "(meth)acrylamide and its derivatives." In this specification, the term "molecular weight" means the sum of the atomic weights of the elements that constitute the molecules of a substance. In this specification, the term "polymerizable monomer" is used to mean a polymerizable compound that is polymerized by a polymerization initiator (B) described later, and may also be expressed as a "polymerizable compound". The dental curable composition which is one embodiment of the present invention contains a polymerizable monomer which contains a polyalkylene di(meth)acrylic acid ester-based monomer (A). In this specification, unless otherwise specified, the terms "hardenable" and "storage stability" refer to the "hardenable" and "storage stability" of the dental hardenable composition which is one embodiment of the present invention. In addition, in this specification, unless otherwise specified, the term "ion-releasing" refers to "fluoride ion-releasing" and "calcium ion-releasing" of a cured product of the dental hardenable composition which is one embodiment of the present invention. In this specification, unless otherwise specified, the terms "mechanical strength" and "strength" refer to the "flexural strength" and "flexural modulus" of the cured product of the dental curable composition which is one embodiment of the present invention. In addition, in this specification, unless otherwise specified, the expression "adhesion durability" refers to the "adhesion durability" of a cured product of the dental hardenable composition which is one embodiment of the present invention.

[0011] [Dental curable composition] The dental curable composition according to one embodiment of the present invention contains a polyalkylene di(meth)acrylic acid ester monomer (A) (hereinafter, also referred to simply as "component (A)"), a polymerization initiator (B) (hereinafter, also referred to simply as "component (B)"), and an ion-releasing compound (C) (hereinafter, also referred to simply as "component (C)").

[0012] In addition, the dental curable composition preferably further contains one or more selected from the group consisting of a (meth)acrylic monomer (D) containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule (hereinafter also referred to simply as "component (D)"), a polymerizable monomer (E) other than components (A) and (D) (hereinafter also referred to simply as "component (E)"), a polymerization accelerator (F) (hereinafter also referred to simply as "component (F)"), and a filler (G) (hereinafter also referred to simply as "component (G)"), and more preferably contains components (D), (E), (F) and (G). Hereinafter, each component contained in the dental curable composition according to one embodiment of the present invention will be described.

[0013] <Polyalkylene di(meth)acrylate monomer (A)> The polyalkylene di(meth)acrylic acid ester-based monomer (A) is used in the dental hardenable composition in order to impart a discharge force reducing effect, ion releasing property, and adhesion durability to a cured product of the dental hardenable composition. It is presumed that a continuous phase of polyalkylene chains is formed in the cured product, and that the ions of the ion-releasing compound are coordinated with an appropriate strength by ether bonds, facilitating the movement of the ions within the phase. The polyalkylene chains must have an appropriate molecular length to exhibit high ion release properties and the strength, water resistance, and adhesive durability of the cured product. If the polyalkylene chain is too short, the strength, water resistance, and adhesion durability are excellent, but sufficient ion release properties are not obtained. The strength, water resistance, and adhesion durability are achieved due to a high crosslink density, but it is presumed that the polyalkylene chain is too short, making it difficult to form a continuous phase of the polyalkylene chain, and thus making it difficult to obtain ion release properties. On the other hand, if the polyalkylene chain is too long, not only do the strength, water resistance, and adhesion durability decrease, but ion release properties are also not obtained. The decrease in strength, water resistance, and adhesion durability is presumably due to the fact that the longer the polyalkylene chain, the looser the crosslinked structure becomes, resulting in increased softness and polarity. It is difficult to speculate as to the reason why ion release cannot be obtained, but it is assumed that the phase structure has an influence. In addition, the polyalkylene di(meth)acrylic acid ester monomer (A) does not bond strongly with ions to form a strong network, unlike hydroxyl groups or acidic groups, and coordinates with ions with moderate strength, so that the dental curable composition can suppress the decrease in operability due to the increase in viscosity. Therefore, the ejection force does not increase too much, and the ejection property is excellent.

[0014] Component (A) is a compound represented by the following general formula [I]. [ka] In the formula, R 1 is a hydrocarbon group having 2 to 4 carbon atoms, and R 2 and R 3 each independently represents a hydrogen atom or a methyl group, and n must be an integer of 4 to 12. When n is 4 to 12, the resulting dental curable composition exhibits high ion release properties, strength, water resistance, and adhesion durability.

[0015] The hydrocarbon group having 2 to 4 carbon atoms is preferably an alkyl group. Examples of the alkyl group include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a cyclopropyl group, and an ethyl group and an n-propyl group are preferred.

[0016] n is preferably 5 or more in terms of providing a better balance between ion release property, water resistance, and adhesion durability, and is more preferably 6 or more, and even more preferably 7 or more, in terms of providing a better effect of reducing the ejection force. In addition, n is preferably 11 or less in terms of achieving a better balance between ion release property, water resistance, and adhesion durability, and is more preferably 10 or less in terms of achieving a better effect of reducing the ejection force, and is even more preferably 10 or less.

[0017] Examples of the polyalkylene di(meth)acrylic acid ester monomer (A) include polyethylene glycol di(meth)acrylates having n=4 to 12, such as tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, undecaethylene glycol di(meth)acrylate, and dodecaethylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate, pentapropylene glycol di(meth)acrylate, hexapropylene glycol di(meth)acrylate, heptapropylene glycol di(meth)acrylate, and octapropylene glycol di(meth)acrylate; Examples of the polybutylene glycol di(meth)acrylates include polypropylene glycol di(meth)acrylates having n=4 to 12, such as (meth)acrylate, nonapropylene glycol di(meth)acrylate, decapropylene glycol di(meth)acrylate, undecapropylene glycol di(meth)acrylate, and dodecapropylene glycol di(meth)acrylate; and polybutylene glycol di(meth)acrylates having n=4 to 12, such as tetrabutylene glycol di(meth)acrylate, pentabtylene glycol di(meth)acrylate, hexabtylene glycol di(meth)acrylate, heptabtylene glycol di(meth)acrylate, octabtylene glycol di(meth)acrylate, nonabtylene glycol di(meth)acrylate, decabutylene glycol di(meth)acrylate, undecabutylene glycol di(meth)acrylate, and dodecabutylene glycol di(meth)acrylate. These may be used alone or in combination of two or more. Among these, from the viewpoint of excellent ion release properties of the dental curable composition, tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, undecaethylene glycol di(meth)acrylate, and dodecaethylene glycol di(meth)acrylate are preferred. Of these, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, and decaethylene glycol di(meth)acrylate are more preferred, and from the standpoint of excellent discharge force reduction effect and adhesion durability, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, and decaethylene glycol di(meth)acrylate are even more preferred, and nonaethylene glycol di(meth)acrylate is the most preferred.

[0018] The content of component (A) in the dental curable composition is preferably 1 to 90 parts by mass, and from the viewpoint of excellent ion release properties, more preferably 5 to 60 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers. Furthermore, the content of component (A) is preferably 1 mass% or more in terms of excellent ion release properties when combined with component (C) in 100 mass% of the dental curable composition, and is more preferably 2 mass% or more, and even more preferably 3 mass% or more, in terms of excellent discharge force reduction effect and adhesion durability. Furthermore, the content of component (A) is preferably 30 mass% or less from the viewpoint of excellent ion release properties when combined with component (C) in 100 mass% of the dental curable composition, and is more preferably 25 mass% or less, and even more preferably 20 mass% or less, from the viewpoint of excellent discharge force reduction effect and adhesion durability.

[0019] <Polymerization initiator (B)> The polymerization initiator (B) can be selected from polymerization initiators used in general industrial applications, and among them, polymerization initiators used for dental applications are preferably used. The polymerization initiator (B) preferably contains at least one selected from the group consisting of a photopolymerization initiator (B-1) and a chemical polymerization initiator (B-2), more preferably contains at least a photopolymerization initiator (B-1), and may contain both a photopolymerization initiator (B-1) and a chemical polymerization initiator (B-2).

[0020] Examples of the photopolymerization initiator (B-1) include (bis)acylphosphine oxides (including salts), thioxanthones (including salts such as quaternary ammonium salts), ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, etc. These may be used alone or in combination of two or more.

[0021] Among these photopolymerization initiators (B-1), it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides and α-diketones, which provides a curable composition that is excellent in photocurability in the visible light region and near ultraviolet region and exhibits sufficient photocurability when any of the light sources, such as a halogen lamp, a light-emitting diode (LED), and a xenon lamp, is used.

[0022] Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethylphenyl)phosphonate, sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, potassium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, and ammonium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide.

[0023] Of the (bis)acylphosphine oxides, examples of the bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,3,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0024] Further, examples of the (bis)acylphosphine oxides include the compounds described in JP-A-2000-159621.

[0025] Among these (bis)acylphosphine oxides, it is more preferable to use 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or the sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide as the photopolymerization initiator (B-1).

[0026] Examples of the α-diketones include diacetyl, benzil, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzil, acenaphthenequinone, etc. Among these, camphorquinone is particularly preferred from the viewpoint of having a maximum absorption wavelength in the visible light region.

[0027] As the chemical polymerization initiator (B-2), an organic peroxide is preferably used. The organic peroxide used as the chemical polymerization initiator (B-2) is not particularly limited, and known organic peroxides can be used. Representative organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates. These may be used alone or in combination of two or more.

[0028] Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide.

[0029] Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0030] Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0031] Examples of the dialkyl peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne.

[0032] Examples of the peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, and 4,4-bis(t-butylperoxy)n-butylvalerate.

[0033] Examples of the peroxyester include α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 2,2,4-trimethylpentyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxyisophthalate, di-t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymaleate.

[0034] Examples of the peroxydicarbonate include di(3-methoxybutyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, and diallylperoxydicarbonate.

[0035] Among these organic peroxides, from the viewpoint of the overall balance of safety, curability, and storage stability, the chemical polymerization initiator (B-2) is preferably one selected from hydroperoxides and diacyl peroxides, and more preferably hydroperoxides. Among them, the chemical polymerization initiator (B-2) is preferably one or more selected from the group consisting of benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide, more preferably one or more selected from the group consisting of cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide, and even more preferably 1,1,3,3-tetramethylbutyl hydroperoxide.

[0036] The content of component (B) is not particularly limited, but from the viewpoint of the hardenability of the dental hardenable composition, it is preferably 0.001 to 30 parts by mass per 100 parts by mass of the total amount of polymerizable monomers. By the content of component (B) being 0.001 parts by mass or more, the polymerization proceeds sufficiently and stickiness can be prevented. From this viewpoint, the content of component (B) is more preferably 0.03 parts by mass or more, further preferably 0.05 parts by mass or more, and particularly preferably 0.1 parts by mass or more, based on 100 parts by mass of the total amount of the polymerizable monomers. On the other hand, by making the content of component (B) 30 parts by mass or less, it is possible to prevent precipitation or separation of component (B) from the dental curable composition. From this viewpoint, the content of component (B) is more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 2 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable monomers.

[0037] Furthermore, when component (B) contains a photopolymerization initiator (B-1), the content of the photopolymerization initiator (B-1) is not particularly limited. However, in one embodiment of the dental curable composition, from the viewpoint of making it easier to achieve the effects of the present invention, the content of the photopolymerization initiator (B-1) in component (B) is preferably 60 to 100 mass%, more preferably 70 to 100 mass%, and even more preferably 80 to 100 mass%, of 100 mass% of component (B).

[0038] Furthermore, when component (B) contains a chemical polymerization initiator (B-2), the content of the chemical polymerization initiator (B-2) is not particularly limited. However, in one embodiment of the dental curable composition, from the viewpoint of making it easier to achieve the effects of the present invention, the content of the chemical polymerization initiator (B-2) in component (B) is preferably 1 to 80 mass%, more preferably 5 to 60 mass%, and even more preferably 10 to 40 mass%, based on 100 mass% of component (B).

[0039] In one embodiment of the dental curable composition, from the viewpoint of making it easier to achieve the effects of the present invention, the total content of the photopolymerization initiator (B-1) and the chemical polymerization initiator (B-2) in component (B) is preferably 60 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 80 to 100 mass%, and may be 100 mass%, based on 100 mass% of component (B).

[0040] <Ion-releasing compound (C)> The dental hardenable composition contains an ion-releasing compound (C) for the purpose of imparting acid resistance to tooth structure. Examples of the ion-releasing compound (C) include a fluoride ion-releasing compound, a calcium ion-releasing compound, a zinc ion-releasing compound, a strontium ion-releasing compound, a phosphate ion, a borate ion, and the like. Among these, fluoride ion-releasing compounds, calcium ion-releasing compounds, zinc ion-releasing compounds and strontium ion-releasing compounds are preferred because they have a large effect of imparting acid resistance to teeth, with fluoride ion-releasing compounds and calcium ion-releasing compounds being more preferred, and fluoride ion-releasing compounds being even more preferred. The dental hardenable composition preferably contains at least one selected from the group consisting of a fluoride ion-releasing compound and a calcium ion-releasing compound, more preferably contains at least a fluoride ion-releasing compound, and even more preferably contains both a fluoride ion-releasing compound and a calcium ion-releasing compound.

[0041] Examples of the fluorine ion releasing compound include fluorine ion releasing polymers such as copolymers of (meth)acrylic acid esters and (meth)acrylic acid fluoride; fluorine ion releasing ammonium salts such as ammonium hydrofluoride and cetylamine hydrofluoride; phosphates such as sodium monofluorophosphate; lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, aluminum fluoride, manganese (II) fluoride, iron (II) fluoride, iron (III) fluoride, cobalt (II) fluoride, copper (II) fluoride, zinc fluoride, antimony (III) fluoride, lead (II) fluoride, silver (I) fluoride, cadmium fluoride, sulphur fluoride, and the like. Metal fluorides such as tin(II), tin(IV) fluoride, silver diammine fluoride, sodium hydrogen fluoride, potassium hydrogen fluoride, sodium fluorophosphate, potassium hexafluorotitanate, sodium hexafluorosilicate, sodium hexafluorophosphate, sodium hexafluorotin(IV), hexafluorostannate(IV) alanine, sodium pentafluorodistannate(II), and potassium hexafluorozirconate; fluorine-containing glasses such as fluoroaluminosilicate glass, fluoroborosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. These may be used alone or in combination of two or more.

[0042] Among these, as the fluorine ion releasing compound, from the viewpoints of excellent ion releasing properties and ease of forming an acid-resistant layer, sodium fluoride, calcium fluoride, strontium fluoride, zinc fluoride, fluoroborosilicate glass, fluoroaluminosilicate glass, and calcium fluoroaluminosilicate glass are preferred, with sodium fluoride, zinc fluoride, and fluoroaluminosilicate glass being more preferred.

[0043] Examples of the calcium ion releasing compound include calcium silicate glass, tetracalcium phosphate, anhydrous calcium hydrogen phosphate, tricalcium phosphate, anhydrous calcium dihydrogen phosphate, amorphous calcium phosphate, acidic calcium pyrophosphate, calcium hydrogen phosphate dihydrate, and calcium dihydrogen phosphate monohydrate, and other phosphorus-containing calcium salts; calcium hydroxide, calcium oxide, calcium chloride, calcium nitrate, calcium acetate, calcium lactate, calcium citrate, calcium metasilicate, dicalcium silicate, tricalcium silicate, and calcium carbonate, and other phosphorus-free calcium salts. These may be used alone or in combination of two or more.

[0044] As the calcium ion-releasing compound, from the viewpoints of excellent ion-releasing properties and ease of strengthening tooth structure, calcium silicate glass, tetracalcium phosphate, anhydrous calcium monohydrogen phosphate, tricalcium phosphate, anhydrous calcium dihydrogen phosphate, amorphous calcium phosphate, calcium hydroxide, calcium oxide, calcium metasilicate, dicalcium silicate, and tricalcium silicate are preferred, and calcium silicate glass, tetracalcium phosphate, anhydrous calcium monohydrogen phosphate, anhydrous calcium dihydrogen phosphate, and amorphous calcium phosphate are more preferred.

[0045] In order to adjust the miscibility with component (A), component (C) may be surface-treated in advance with a known surface treatment agent such as polysiloxane, polyethylene glycol, fatty acid amide, silane coupling agent, etc., within the range that does not impair the ion-releasing property. However, it is preferable not to carry out a strong coating treatment such as a silica coat that covers the ion-releasing compound, or to form a core-shell structure, etc., since these impair the ion-releasing property.

[0046] The surface treatment method can be any known method without any particular limitation, and examples thereof include (1) a method in which a layer made of a silanol compound is formed on the surface of an ion-releasing compound (C), and then the silanol groups are subjected to intermolecular dehydration condensation; and (2) a method in which a hydrolyzable silane compound is (partially) hydrolyzed to previously form an oligomer by intermolecular dehydration condensation of the silanol groups, and a powdered ion-releasing compound (C) is added to the siloxane oligomer to form a layer made of the siloxane oligomer on the surface of the ion-releasing compound (C), and then the siloxane oligomer is subjected to intermolecular dehydration condensation to polymerize.

[0047] In the method (1), first, a hydrolyzable silane compound and a necessary amount of water are added to a water-miscible organic solvent such as methanol, ethanol, or t-butanol, and the hydrolyzable silane compound is (partially) hydrolyzed in the presence of an acid catalyst to prepare an organic solution containing a silanol compound that is the hydrolysis product. Examples of the silane compound include vinyl group-containing silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and vinyltri(β-methoxyethoxy)silane; (meth)acryloyl group-containing silane compounds such as γ-(meth)acryloyloxypropyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, γ-(meth)acryloyloxypropylmethyldiethoxysilane, and γ-(meth)acryloyloxypropyldimethylmonomethoxysilane; amino group-containing silane compounds such as γ-aminopropyltriethoxysilane; epoxy group-containing silane compounds such as γ-glycidoxypropyltrimethoxysilane; and mercapto group-containing silane compounds such as γ-mercaptopropyltrimethoxysilane. The organic solution containing the silanol compound can also be prepared by adding an excess of water to a hydrolyzable silane compound, partially hydrolyzing it in the presence of an acid catalyst to prepare an aqueous solution containing the silanol compound, and then extracting the silanol compound in the aqueous solution using an organic solvent that is not miscible with water, such as ethyl acetate, ethyl ether, chloroform, or methylene chloride, as an extracting solution. Next, a powdered ion-releasing compound (C) is added to the organic solution obtained by these methods, and the organic solvent is evaporated by heat treatment or reduced pressure treatment to obtain an ion-releasing compound (C) consisting of composite particles in which a layer of the silanol compound is attached to the surface of the ion-releasing compound (C). Next, an acid or base is added as necessary, and the ion-releasing compound (C) is heated to dehydrate and condense the silanol groups between molecules, thereby producing an ion-releasing compound (C) consisting of composite particles in which a layer of polysiloxane is formed on the surface of the ion-releasing compound (C).

[0048] In the method (2), a predetermined amount of water is first added to a hydrolyzable silane compound, and in the presence of an acid catalyst, the by-product alcohol is distilled off while the compound is (partially) hydrolyzed and dehydrated to produce a siloxane oligomer. A powdered ion-releasing compound (C) is added to the siloxane oligomer to form a layer of the siloxane oligomer on the particle surface, and an acid or base is added as necessary, followed by heat treatment to cause intermolecular dehydration condensation of the silanol groups in the siloxane oligomer, producing an ion-releasing compound (C) consisting of a composite particle in which a layer of polysiloxane is formed on the surface of a base particle consisting of the ion-releasing compound (C).

[0049] The shape of component (C) is not particularly limited, and may be any particulate shape such as spherical, needle-like, plate-like, crushed, or scaly. Also, it may be dissolved in a polymerizable monomer or the like. When component (C) is particulate, the average primary particle size is preferably 0.001 to 10 μm, more preferably 0.005 to 5.0 μm, even more preferably 0.01 to 4.0 μm, and particularly preferably 0.05 to 1.0 μm, from the viewpoints of the handleability of the dental curable composition and the ion release, mechanical strength, and transparency of the cured product thereof. In this specification, the average primary particle size of component (C) is determined by observation with an optical microscope or an electron microscope. Specifically, observation with an optical microscope is convenient for measuring particle sizes of 100 nm or more, and observation with an electron microscope is convenient for measuring particle sizes of less than 100 nm.

[0050] The content of component (C) is not particularly limited, but from the viewpoints of the handleability of the resulting composition and the ion release properties of the cured product, it is preferably 1.0 to 400 parts by mass, more preferably 10 to 300 parts by mass, and even more preferably 20 to 200 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers. The content of component (C) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on 100% by mass of the dental curable composition. The content of component (C) is preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, based on 100% by mass of the dental curable composition.

[0051] Furthermore, the total amount of component (A), component (B), and component (C) in the dental hardenable composition is not particularly limited as long as the effects of the present invention are achieved. From the viewpoint of making it easier to achieve the effects of the present invention, however, the total amount is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the dental hardenable composition. The total amount of components (A), (B) and (C) is 100% by mass or less, preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0052] <(Meth)acrylic monomer (D) containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule> The (meth)acrylic monomer (D) containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule may be used in the dental hardenable composition to impart strength to a cured product of the dental hardenable composition and to enhance ion release properties by coexisting with component (A). The urethane bonds contained in the (meth)acrylic monomer (D) can form hydrogen bonds with each other, and in addition, when they coexist with components (A) and (C), they form hydrogen bonds, which not only impart strength but also promote the propagation of ions due to their strong polarity, thereby imparting ion release properties. The (meth)acrylic monomer (D) may be used alone or in combination of two or more kinds.

[0053] Component (D) can be easily synthesized, for example, by subjecting a compound containing an isocyanate having an alkylene skeleton or a phenylene skeleton to an addition reaction with a (meth)acrylate compound having a hydroxyl group (—OH). Also, it can be easily synthesized by addition reaction of a polyol containing a polymer skeleton, a compound having an isocyanate group (-NCO), and a (meth)acrylate compound having a hydroxyl group (-OH). Among these, it is preferred that component (D) does not contain a polymer skeleton, since the dental hardenable composition will have excellent strength in the cured product. Furthermore, from the same viewpoint and from the viewpoint of being more effective in reducing the ejection force, component (D) is preferably a compound having a molecular weight of 1,000 or less, more preferably a compound having a molecular weight of 750 or less, and even more preferably a compound having a molecular weight of 500 or less.

[0054] Examples of compounds having an isocyanate group include methylene diisocyanate (abbreviation: MDI), hexamethylene diisocyanate (abbreviation: HDI), isophorone diisocyanate (abbreviation: IPDI), trimethylhexamethylene diisocyanate (abbreviation: TMHMDI), tricyclodecane diisocyanate (abbreviation: TCDDI), adamantane diisocyanate (abbreviation: ADI), tolylene diisocyanate (abbreviation: TDI), xylylene diisocyanate (abbreviation: XDI), and diphenylmethane diisocyanate (abbreviation: DPMDI), etc. Among these, from the viewpoint of excellent strength of the cured product of the dental curable composition, IPDI, TMHMDI, and TCDDI are preferred, and TMHMDI is more preferred.

[0055] Examples of the (meth)acrylate compound having a hydroxyl group include hydroxy(meth)acrylate compounds such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 10-hydroxydecyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, glycerin mono(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl(meth)acrylate, 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pentaerythritol tri(meth)acrylate, and dipentaerythritol tri- or tetra(meth)acrylate. These may be used alone or in combination of two or more. Among these, from the viewpoint of excellent curability of the dental curable composition, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth)acrylate are preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.

[0056] The addition reaction between a compound having an isocyanate group and a (meth)acrylate compound having a hydroxyl group can be carried out according to a known method, and there is no particular limitation.

[0057] Examples of the component (D) that does not contain a polymer structure include 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (abbreviation: UDMA), 2,4-tolylenebis(2-carbamoyloxyethyl)dimethacrylate, bishydroxyethyl methacrylate-isophorone diurethane, 2,4-tolylenebis(2-carbamoyloxyethyl)dimethacrylate, N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate (abbreviation: U4TH), hexamethylenebis{2-carbamoyloxy-3-phenoxypropyl}dimethacrylate, 2,4-tolylenebis(2-carbamoyloxyethyl)hexamethacrylate, etc. These may be used alone or in combination of two or more. Among these, UDMA and U4TH are preferred from the viewpoint of improving strength and ion release properties, and UDMA is more preferred from the viewpoints of superior adhesion durability and superior effect of reducing ejection force.

[0058] In the dental hardenable composition containing component (D), the content of component (D) is preferably 20 to 95 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomers, from the viewpoint of excellent effect of reducing the ejection force, and more preferably 30 to 90 parts by mass, and even more preferably 40 to 80 parts by mass, from the viewpoint of excellent ion release property. The content of component (D) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, based on 100% by mass of the dental hardenable composition. The content of component (D) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the dental curable composition.

[0059] In an embodiment containing a (meth)acrylic monomer (D), the dental curable composition acts integrally with component (A) and, from the viewpoint of achieving an excellent balance between strength and sustained ion release property, it is preferable that the value represented by the content of the (meth)acrylic monomer (D) / the content of the polyalkylene di(meth)acrylic acid ester monomer (A) is 1 or more. In addition, since the content of the (meth)acrylic monomer (D) is greater than the content of the polyalkylene di(meth)acrylic acid ester monomer (A), the strength, adhesiveness and adhesion durability are superior. Furthermore, the value expressed by the content of component (D) / the content of component (A) is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.2 or more.

[0060] <Polymerizable monomer (E) other than polyalkylene di(meth)acrylic acid ester monomer (A) and (meth)acrylic monomer (D) containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule> The dental curable composition of the present invention may contain a polymerizable monomer (E) other than the polyalkylene di(meth)acrylic acid ester monomer (A) and the (meth)acrylic monomer (D) containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule. In other words, the polymerizable monomer (E) is a polymerizable monomer that does not belong to either component (A) or component (D). As the polymerizable monomer (E) used in the dental curable composition of the present invention, a radically polymerizable monomer is suitably used. Specific examples of the radical polymerizable monomer in the polymerizable monomer (E) include (meth)acrylate polymerizable monomers, (meth)acrylamide polymerizable monomers, esters such as α-cyanoacrylic acid, (meth)acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, and styrene derivatives. As the polymerizable monomer (E), from the viewpoint of curability, (meth)acrylate polymerizable monomers and (meth)acrylamide polymerizable monomers are preferred.

[0061] The polymerizable monomer (E) in the present invention is exemplified by a monofunctional monomer having one polymerizable group and a polyfunctional monomer having a plurality of polymerizable groups.

[0062] Examples of the monofunctional monomer having one polymerizable group include a monofunctional (meth)acrylate polymerizable monomer and a monofunctional (meth)acrylamide polymerizable monomer.

[0063] Examples of the monofunctional (meth)acrylate polymerizable monomer include an aliphatic (meth)acrylate polymerizable monomer and an aromatic (meth)acrylate polymerizable monomer.

[0064] Examples of aromatic (meth)acrylate polymerizable monomers include acidic group-containing aromatic (meth)acrylates such as 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate;o-phenylphenol (meth)acrylate, m-phenylphenol (meth)acrylate, p-phenylphenol (meth)acrylate, methoxylated-o-phenylphenol (meth)acrylate, methoxylated-m-phenylphenol (meth)acrylate, methoxylated-p-phenylphenol (meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, ethoxylated-m-phenylphenol (meth)acrylate, ethoxylated-p-phenylphenol (meth)acrylate, Propoxylated-o-phenylphenol (meth)acrylate, propoxylated-m-phenylphenol (meth)acrylate, propoxylated-p-phenylphenol (meth)acrylate, butoxylated-o-phenylphenol (meth)acrylate, butoxylated-m-phenylphenol (meth)acrylate, butoxylated-p-phenylphenol (meth)acrylate, o-phenoxybenzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, p-phenoxybenzyl (meth)acrylate , 2-(o-phenoxyphenyl)ethyl (meth)acrylate, 2-(m-phenoxyphenyl)ethyl (meth)acrylate, 2-(p-phenoxyphenyl)ethyl (meth)acrylate, 3-(o-phenoxyphenyl)propyl (meth)acrylate, 3-(m-phenoxyphenyl)propyl (meth)acrylate, 3-(p-phenoxyphenyl)propyl (meth)acrylate, 4-(o-phenoxyphenyl)butyl (meth)acrylate, 4-(m-phenoxyphenyl)butyl (meth)acrylate Examples of aromatic ring-containing (meth)acrylates include 4-(p-phenoxyphenyl)butyl (meth)acrylate, 5-(o-phenoxyphenyl)pentyl (meth)acrylate, 5-(m-phenoxyphenyl)pentyl (meth)acrylate, 5-(p-phenoxyphenyl)pentyl (meth)acrylate, 6-(o-phenoxyphenyl)hexyl (meth)acrylate, 6-(m-phenoxyphenyl)hexyl (meth)acrylate, and 6-(p-phenoxyphenyl)hexyl (meth)acrylate.

[0065] Examples of the aliphatic (meth)acrylate polymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and isobornyl (meth)acrylate. alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, and other hydroxyl group-containing (meth)acrylates;2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate Hydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, bihydrogen phosphate, Bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di Examples of the acidic group-containing (meth)acrylates include (meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, and bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogen phosphate; and silyl group-containing (meth)acrylates include 3-(meth)acryloyloxypropyl trimethoxysilane and 11-(meth)acryloyloxyundecyl trimethoxysilane.

[0066] Examples of monofunctional (meth)acrylamide polymerizable monomers include (meth)acrylamide compounds having a cyclic structure such as N-(meth)acryloylmorpholine; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide, N,N-di-n-hexyl(meth)acrylamide, N,N-di-n-octyl(meth)acrylamide, N,N-di-2-ethylhexyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, and N,N-(dihydroxyethyl)acrylamide. These may be used alone or in combination of two or more. Among the monofunctional monomers, (meth)acrylamide-based polymerizable monomers are preferred because of their excellent curability, and among these, N-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide are more preferred.

[0067] Examples of the polyfunctional monomer include bifunctional polymerizable monomers of aromatic compounds, bifunctional polymerizable monomers of aliphatic compounds, and trifunctional or higher polymerizable monomers.

[0068] Examples of aromatic bifunctional polymerizable monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-acryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis[4-(3-methacryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, and 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane. , 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, etc. These may be used alone or in combination of two or more. Among these, 2,2-bis[4-(3-methacryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA") and 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane are preferred because of their excellent curability and strength of the cured product. Among 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (a compound having an average added mole number of ethoxy groups of 2.6 (commonly known as "D2.6E")) is preferred.

[0069] Examples of the aliphatic compound-based bifunctional polymerizable monomer include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (n=13 or more), 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-ethyl-1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane. These may be used alone or in combination of two or more.

[0070] Examples of the trifunctional or higher polymerizable monomer include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, 1,7-diacryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxaheptane, and the like.

[0071] When the polymerizable monomer (E) contains an aliphatic compound-based bifunctional (meth)acrylate polymerizable monomer, or an aromatic compound-based bifunctional (meth)acrylate polymerizable monomer and a monofunctional (meth)acrylate polymerizable monomer, the content of the bifunctional (meth)acrylate polymerizable monomer is preferably 45 to 100 parts by mass, more preferably 50 to 90 parts by mass, and even more preferably 55 to 85 parts by mass in the total amount of 100 parts by mass of the polymerizable monomer (E). When the polymerizable monomer (E) contains a monofunctional (meth)acrylate polymerizable monomer, the content of the monofunctional (meth)acrylate polymerizable monomer is preferably 10 to 100 parts by mass, more preferably 30 to 100 parts by mass, and even more preferably 50 to 100 parts by mass in the total amount of 100 parts by mass of the polymerizable monomer (E). In this specification, the content of a certain polymerizable monomer in the total amount of 100 parts by mass of the polymerizable monomer components means the content (mass%) of the polymerizable monomer when the total amount of the polymerizable monomer components is converted to 100 mass%, and therefore the total amount of each polymerizable monomer component does not exceed 100 parts by mass. The content of the polymerizable monomer (E) is preferably from 2 to 45 mass %, more preferably from 3 to 40 mass %, and even more preferably from 4 to 35 mass %, based on 100 mass % of the dental curable composition.

[0072] <Polymerization accelerator (F)> The dental curable composition preferably further contains a polymerization accelerator (F). The polymerization accelerator (F) is roughly classified into a polymerization accelerator (F-1) that reacts with a photopolymerization initiator (B-1) to accelerate photopolymerization, and a chemical polymerization accelerator (F-2) that reacts with a chemical polymerization initiator (B-2).

[0073] Examples of the polymerization accelerator (F-1) include amines, aldehydes, and triazine compounds. These may be used alone or in combination of two or more.

[0074] The amines used as the polymerization accelerator (F-1) are classified into aliphatic amines and aromatic amines. Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; and tertiary aliphatic amines such as N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine.

[0075] Examples of aromatic amines include alkylaminobenzoate esters such as ethyl 4-(N,N-dimethylamino)benzoate, methyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, butyl 4-(N,N-dimethylamino)benzoate, and 2-(methacryloyloxy)ethyl 4-(N,N-dimethylamino)benzoate; and 4-(N,N-dimethylamino)benzophenone.

[0076] Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives, etc. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, p-n-octyloxybenzaldehyde, etc.

[0077] Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis (trichloromethyl)-s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6 -Bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,Examples of the 6-bis(trichloromethyl)-s-triazine include 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine.

[0078] Examples of the chemical polymerization accelerator (F-2) include amines, sulfinic acid and its salts, sulfites, hydrogen sulfites, aldehydes, thiourea compounds, organic phosphorus compounds, borate compounds, barbituric acid compounds, triazine compounds, vanadium compounds, copper compounds, tin compounds, cobalt compounds, halogen compounds, and thiol compounds. These may be used alone or in combination of two or more.

[0079] The amines used in the chemical polymerization accelerator (F-2) are classified into aliphatic amines and aromatic amines. Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; and tertiary aliphatic amines such as N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine.

[0080] Examples of aromatic amines include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-di Examples of aromatic amines having an alkylaniline skeleton include methylaniline, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, and N,N-diethyl-p-toluidine.

[0081] Examples of sulfinic acid and its salts include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, and 2,4,6-trimethylbenzenesulfinate. Examples of the sulfinate include calcium sulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, and calcium 2,4,6-triisopropylbenzenesulfinate.

[0082] Examples of sulfites and hydrogen sulfites include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, and the like.

[0083] Examples of the thiourea compound include 1-(2-pyridyl)-2-thiourea, thiourea, methylthiourea, ethylthiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea, 3,3-dimethylethylenethiourea, 4,4-dimethylethylenethiourea, etc. Among these, from the viewpoint of the hardening property of the dental hardenable composition, at least one selected from the group consisting of 1-(2-pyridyl)-2-thiourea and 4,4-dimethylethylenethiourea is preferable.

[0084] Examples of the organic phosphorus compound include triphenylphosphine, 2-methyltriphenylphosphine, 4-methyltriphenylphosphine, 2-methoxytriphenylphosphine, 4-methoxytriphenylphosphine, tri-n-butylphosphine, triisobutylphosphine, and tri-t-butylphosphine.

[0085] The borate compound is preferably an aryl borate compound. Specific examples of the aryl borate compound that can be suitably used include borate compounds having one aryl group in one molecule, such as trialkylphenyl boron, trialkyl(p-chlorophenyl) boron, trialkyl(p-fluorophenyl) boron, trialkyl[3,5-bis(trifluoromethyl)phenyl] boron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl] boron, trialkyl(p-nitrophenyl) boron, trialkyl(m-nitrophenyl) boron, trialkyl(p-butylphenyl) boron, trialkyl(m-butylphenyl) boron, trialkyl( Examples of the alkyl group include trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like), as well as salts thereof (sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like).

[0086] Examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi[3,5-bis(trifluoromethyl)phenyl]boron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, and dialkyldi(p-butyloxyphenyl)boron. , dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like), as well as salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like).

[0087] Examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri[3,5-bis(trifluoromethyl)phenyl]boron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri(p ... Examples of the alkyl group include monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (wherein the alkyl group is one selected from an n-butyl group, an n-octyl group, an n-dodecyl group, etc.), as well as salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.).

[0088] Examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis[3,5-bis(trifluoromethyl)phenyl]boron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis(m-nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p-octyloxyphenyl)boron, tetrakis(m-octyloxyphenyl)boron,

[0036] Examples of suitable aryloxyphenyls include (p-phenyl)boron, (p-fluorophenyl)triphenylboron, [3,5-bis(trifluoromethyl)phenyl]triphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron and (p-octyloxyphenyl)triphenylboron, as well as salts thereof (sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, etc.).

[0089] Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. Moreover, these aryl borate compounds can be used alone or in combination of two or more kinds.

[0090] Examples of barbituric acid compounds 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-5-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, and 1-cyclohexyl-1-ethylbarbituric acid. , 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and thiobarbituric acids, and salts thereof (particularly alkali metals or alkaline earth metals are preferred). Examples of the salts of these barbituric acid compounds include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, sodium 1-cyclohexyl-5-ethylbarbiturate, and the like.

[0091] The vanadium compound is preferably a trivalent and / or pentavalent vanadium compound. Examples of trivalent and / or pentavalent vanadium compounds include divanadium tetroxide (IV), vanadyl acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxo-bis(1-phenyl-1,3-butanedionato)vanadium (IV), bis(maltolato)oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V). Among these, vanadyl acetylacetonate (IV) is preferred from the viewpoint of the hardening property of the dental hardenable composition.

[0092] Examples of the copper compound include copper acetylacetonate, copper (II) acetate, copper oleate, copper (II) chloride, copper (II) bromide, etc. Among these, at least one selected from the group consisting of copper acetylacetonate and copper (II) acetate is preferred from the viewpoint of the hardenability of the dental hardenable composition.

[0093] Examples of the tin compound include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, di-n-butyltin dilaurate, etc. Among them, at least one selected from the group consisting of di-n-octyltin dilaurate and di-n-butyltin dilaurate is preferably used.

[0094] Examples of cobalt compounds include cobalt acetylacetonate, cobalt acetate, cobalt oleate, cobalt chloride, and cobalt bromide.

[0095] Examples of the halogen compound that can be suitably used include dilauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, and dilauryl dimethyl ammonium bromide.

[0096] Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0097] Among these polymerization accelerators (F), at least one selected from the group consisting of amines, thiourea compounds, vanadium compounds, and copper compounds is preferred, and among these, at least one selected from the group consisting of 1-(2-pyridyl)-2-thiourea, N,N-di(2-hydroxyethyl)-p-toluidine, ethyl 4-(N,N-dimethylamino)benzoate, 4,4-dimethylethylenethiourea, vanadyl acetylacetonate (IV), copper acetylacetonate, and cupric acetate is more preferred as component (F).

[0098] The content of component (F) in the dental hardenable composition is not particularly limited, but from the viewpoint of the hardenability of the dental hardenable composition, it is preferably 0.001 to 30 parts by mass per 100 parts by mass of the total amount of polymerizable monomers. By the content of the polymerization accelerator (F) being 0.001 parts by mass or more, polymerization can be sufficiently advanced and stickiness can be prevented. From this viewpoint, the content of the component (F) is more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and particularly preferably 0.3 parts by mass or more, relative to 100 parts by mass of the total amount of the polymerizable monomer. On the other hand, by the content of the component (F) being 30 parts by mass or less, precipitation of the component (F) from the dental hardenable composition can be prevented. From this viewpoint, the content of the component (F) is more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 5.0 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable monomer.

[0099] In the present invention, the chemical polymerization initiator (B-2) and the chemical polymerization promoter (F-2) may be combined to form a redox polymerization initiator. In this case, from the viewpoint of storage stability, the chemical polymerization initiator (B-2) and the chemical polymerization accelerator (F-2) are preferably stored in separate containers. In this case, the dental hardenable composition is preferably provided as a dental hardenable composition of a separate package type, which is packaged at least in a first material containing the chemical polymerization initiator (B-2) and a second material containing the polymerization accelerator (F). Moreover, the dental hardenable composition is more preferably provided as a kit to be used in the form of a two-material type consisting of the first material and the second material. In this case, the dental hardenable composition is further preferably provided as a kit to be used in the form of a two-paste type in which both the first material and the second material are in a paste form. When the dental hardenable composition is provided as a kit in the form of a two-paste type, the pastes are stored in a state in which they are isolated from each other, and the two pastes are kneaded together immediately before use to allow chemical polymerization to proceed. In addition, when the dental hardenable composition further contains a photopolymerization initiator (B-1), it is preferable to harden the dental hardenable composition by allowing photopolymerization to proceed in addition to chemical polymerization. In one embodiment of the separately packaged dental hardenable composition which is packaged into the first material and the second material, from the viewpoint of improving the ion release properties from the cured product of the dental hardenable composition, it is more preferable that the first material further contains the component (A), and it is even more preferable that the first material further contains both the component (A) and the component (C).

[0100] <Filler (G)> It is preferable that the dental curable composition further contains a filler (G) from the viewpoints of adjusting the paste properties of the dental curable composition before curing, imparting X-ray contrast properties to the cured product, or further improving the strength of the cured product. The filler (G) is other than those included in the ion-releasing compound (C). Examples of fillers that can be used as component (G) include organic fillers, inorganic fillers, and organic-inorganic composite fillers, etc. The filler (G) may be used alone or in combination of two or more kinds.

[0101] Examples of the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyester, polyamide, polycarbonate, polyphenylene ether, polyoxymethylene, polyvinyl chloride, polystyrene, polyethylene, polypropylene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, etc. These may be used alone or in combination of two or more. The shape of the organic filler is not particularly limited, and amorphous fillers and spherical fillers can be appropriately selected and used, and the particle size of the filler can be appropriately selected and used.

[0102] Examples of inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, etc. These may also be used alone or in combination of two or more. The shape of the inorganic filler is not particularly limited, and amorphous fillers and spherical fillers can be appropriately selected and used, and the particle size of the filler can be appropriately selected and used.

[0103] The inorganic filler may be surface-treated with a known surface treatment agent such as a silane coupling agent before use, if necessary, in order to adjust the miscibility with components (A), (D), and (E). Examples of such surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.

[0104] The surface treatment method can be any known method without any particular limitation. For example, there is a method in which the surface treatment agent is sprayed onto the inorganic filler while vigorously stirring the inorganic filler; a method in which the inorganic filler and the surface treatment agent are dispersed or dissolved in a suitable solvent and then the solvent is removed; or a method in which the alkoxy groups of the surface treatment agent are hydrolyzed in an aqueous solution with an acid catalyst to convert them to silanol groups, which are then attached to the inorganic filler surface in the aqueous solution, and then the water is removed. In any of these methods, the reaction between the inorganic filler surface and the surface treatment agent can be completed by heating in the range of usually 50 to 150°C, thereby performing the surface treatment.

[0105] The organic-inorganic composite filler is obtained by adding a monomer compound to the inorganic filler described above in advance, forming a paste, polymerizing it, and pulverizing it. For example, TMPT filler (trimethylolpropane trimethacrylate and silica filler mixed, polymerized, and pulverized) can be used as the organic-inorganic composite filler. The shape of the organic-inorganic composite filler is not particularly limited, and amorphous fillers, spherical fillers, etc. can be appropriately selected and used, and the particle size of the filler can be appropriately selected and used.

[0106] From the viewpoints of handling of the dental curable composition and mechanical strength and transparency of the cured product thereof, the average primary particle size of component (G) is preferably 0.001 to 10 μm, more preferably 0.005 to 5.0 μm, even more preferably 0.01 to 4.0 μm, and particularly preferably 0.04 to 3.0 μm. In this specification, the average primary particle size of component (G) can be determined by observation with an optical microscope or an electron microscope. Specifically, optical microscope observation is convenient for measuring particle sizes of 100 nm or more, and electron microscope observation is convenient for measuring particle sizes of less than 100 nm.

[0107] Furthermore, from the viewpoints of imparting X-ray contrast properties to the cured product of the dental curable composition and further improving the mechanical strength of the cured product, the amount of component (G) having an average primary particle size of 0.01 μm or more is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, and particularly preferably 98 parts by mass or more, per 100 parts by mass of the total amount of component (G). Moreover, it is particularly preferable that the dental curable composition contains both the component (G) having an average primary particle diameter of 0.01 μm or more, and the component (G) having an average primary particle diameter of less than 0.01 μm.

[0108] The content of component (G) is not particularly limited, but from the viewpoints of the handleability of the dental curable composition and the strength of the cured product thereof, the content is preferably 50 to 500 parts by mass, more preferably 60 to 400 parts by mass, even more preferably 65 to 300 parts by mass, and particularly preferably 70 to 200 parts by mass, relative to 100 parts by mass of the total amount of polymerizable monomers.

[0109] When the dental hardenable composition further contains the components (D), (E), (F) and (G) in addition to the components (A) to (C), the total amount of the components (A) to (G) in the dental hardenable composition is not particularly limited as long as the effects of the present invention are achieved. From the viewpoint of making the effects of the present invention easier to be achieved, the total amount is preferably 80 to 100 mass%, more preferably 85 to 100 mass%, relative to 100 mass% of the dental hardenable composition. From the viewpoint of achieving excellent ion release property, the total amount is still more preferably 90 to 100 mass%, particularly preferably 95 to 100 mass%, and most preferably 98 to 100 mass%.

[0110] <Other additives> Furthermore, other known additives may be blended into the dental hardenable composition as necessary within the range in which the effects of the present invention are achieved. Examples of other additives include polymerization inhibitors other than the above-mentioned components, antioxidants, pigments, dyes, ultraviolet absorbers, organic solvents, thickeners, etc. These may be used alone or in combination of two or more. In addition, in this specification, "other additives" does not include polymerizable monomers.

[0111] Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, and 3,5-di-t-butyl-4-hydroxytoluene. When the dental curable composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.001 to 1.0 part by mass, more preferably 0.005 to 0.5 part by mass, and even more preferably 0.01 to 0.1 part by mass, relative to 100 parts by mass of the total amount of the polymerizable monomers.

[0112] Furthermore, the total amount of other additives is not particularly limited as long as the effects of the present invention are achieved, but from the viewpoint of making it easier to achieve the effects of the present invention, the total amount is preferably 20 mass % or less, more preferably 15 mass % or less, even more preferably 10 mass % or less, particularly preferably 5 mass % or less, and most preferably 2 mass % or less, and may be 0 mass %, based on 100 mass % of the dental hardenable composition.

[0113] In addition, the dental hardenable composition is not particularly limited as long as it contains component (A), component (B), and component (C). However, from the viewpoint of preventing the deterioration of the strength and water resistance of the cured product, as well as the occurrence of cloudiness, it is preferable that the dental hardenable composition does not substantially contain a polycarboxylic acid. In addition, "substantially free of polycarboxylic acid" means that the content of polycarboxylic acid in 100% by mass of the dental hardenable composition is 5.0% by mass or less, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less. From the viewpoint of improving the strength and color tone of the obtained cured product, it is preferable that the dental curable composition contains substantially no water. In addition, "substantially free of water" means that the water content is 5.0 mass % or less, preferably 1.0 mass % or less, more preferably 0.5 mass % or less, even more preferably 0.1 mass % or less, and particularly preferably 0.05 mass % or less, relative to 100 mass % of the dental hardenable composition.

[0114] The dental hardenable composition has excellent ion release properties, mechanical strength, and adhesion durability of the cured product, and therefore can be suitably used in applications where such advantages are utilized. As the above-mentioned applications, the composition can be particularly suitably used as a dental filling and restorative material (dental composite resin, etc.), a dental cement, a dental abutment construction material, and a dental adhesive. In addition, the dental hardenable composition is not particularly limited with respect to the method of mixing the components, etc., except for the above-mentioned points regarding the case where the dental hardenable composition is used in the form of a two-material type consisting of the first material and the second material, and can be produced by a method known to those skilled in the art. EXAMPLES

[0115] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

[0116] Each component used in the examples and comparative examples will be explained below together with its abbreviation.

[0117] [Polyalkylene di(meth)acrylic acid ester monomer (A)] 7PGDMA: Polypropylene glycol dimethacrylate (n=7) (NOF Corporation PDP400N) 9EGDMA: Polyethylene glycol dimethacrylate (n=9) (NOF Corporation PDE400)

[0118] [Polymerization initiator (B)] <Photopolymerization initiator (B-1)> CQ: Camphorquinone <Chemical polymerization initiator (B-2)> THP: 1,1,3,3-tetramethylbutyl hydroperoxide

[0119] [Ion-releasing compound (C)] Compound (C-1): 3-methacryloyloxypropyltrimethoxysilane-treated fluoroaluminosilicate glass "SCHOTT (registered trademark) G018-090 UF0.7" (manufactured by SCHOTT, average primary particle size: 0.7 μm) Compound (C-2): Sodium fluoride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average primary particle size: 2.5 μm) Compound (C-3): Tetracalcium phosphate (manufactured by Pacific Chemical Industries Co., Ltd., average primary particle size: 3.2 μm)

[0120] [(Meth)acrylic monomer (D) containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule] UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (Kyoeisha Chemical Co., Ltd.) U4TH: N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate (Kyoeisha Chemical Co., Ltd.) UA31F Molecular weight 1200: Crystalline polyester-based urethane acrylate oligomer, functional group number 3 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0121] [Polyalkylene di(meth)acrylic acid ester monomers and polymerizable monomers (E) other than (meth)acrylic monomers containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule] D2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6, manufactured by Shin-Nakamura Chemical Co., Ltd.) POBMA: m-phenoxybenzyl methacrylate (Kyoeisha Chemical Co., Ltd.) BMHPE: 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0122] [Polymerization accelerator (F)] PDE: Ethyl 4-(N,N-dimethylamino)benzoate PTU: 1-(2-pyridyl)-2-thiourea VOAA: Vanadyl acetylacetonate(IV)

[0123] Filler Filler (G-1): 3-methacryloyloxypropyltrimethoxysilane-treated barium glass "SCHOTT (registered trademark) 8235 UF2.0" (manufactured by SCHOTT, average primary particle size: 2.0 μm) Filler (G-2): Hydrophilic fumed silica "AEROSIL (registered trademark) 380" (manufactured by Nippon Aerosil Co., Ltd., average primary particle size: 0.007 μm)

[0124] [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene

[0125] [Examples 1 to 17 and Comparative Examples 1 to 7] In each of the Examples and Comparative Examples, the components shown in Tables 1 to 3 below were mixed at room temperature (25°C) to prepare one-component and two-component pastes, thereby obtaining dental curable compositions for each of the Examples and Comparative Examples. When using a one-material dental hardenable composition, a container of dental filling composite resin (product name "Clearfil (registered trademark) Majesty LV", manufactured by Kuraray Noritake Dental Co., Ltd., cylindrical part length: 7.5 cm, inner diameter of opening: 0.8 cm) was used. Furthermore, a guide tip with a length of 1.5 cm and an inner diameter of an opening of 0.8 mm was attached to the tip of the container to prepare a device. When using the two-material dental hardenable composition, a kneading device was used. The kneading device was a polyolefin resin storage container (total volume 5 mL, product code "SDL 005-01-SI", manufactured by Sulzer Mixpac AG (Switzerland)) in which a pair of identical cylinders were arranged in parallel, a mixer attached to the front end of each storage container, and an extrusion device (product code "PED 005-01-SI", manufactured by Sulzer Mixpac AG (Switzerland)) consisting of a pair of cylindrical extrusion members fitted into each storage container from the rear end side of each storage container. By pushing the extrusion member of the kneading device in the two-material type, an equal volume of the paste inside the cylindrical container is collected. The mixer of the kneading device in the two-material type is a mixing tip (product code "ML 2.5-08-S", manufactured by Sulzer Mixpac AG (Switzerland)) with eight stirring blades (elements). The fluoride ion and calcium ion release properties, flexural strength, flexural modulus and adhesion durability of the obtained dental curable compositions were measured or evaluated as follows.

[0126] <Preparation Example 1> A primer for bonding to tooth having the following composition was prepared. Dental bonding primer: MDP: 10-methacryloyloxydecyl dihydrogen phosphate 10 parts by mass HEMA: 2-hydroxyethyl methacrylate 25 parts by weight DMAEMA: N,N-dimethylaminoethyl methacrylate 3.0 parts by weight Purified water: 60 parts by mass VOAA: 0.5 parts by mass BHT: 1.5 parts by mass

[0127] <Discharge performance (discharge force)> As described above, the one-material dental hardenable composition was prepared using an apparatus in which a guide tip with a length of 1.5 cm and an inner diameter of 0.8 mm at the opening was attached to the tip of a Clearfil (registered trademark) Majesty LV container (syringe container). Extrusion was performed using the apparatus, and the paste in the container was discharged from the discharge part through the guide tip. The discharge force at this time (the force required to extrude the paste from the syringe container to the guide tip) was measured using a universal testing machine (manufactured by Shimadzu Corporation, product name "AG-I 100kN"). As described above, the two-material dental hardenable composition was prepared using a kneading device manufactured by Sulzer Mixpac AG (Switzerland). Extrusion was performed using the device, and the paste in the container was discharged from the discharge part through the mixer. The discharge force at this time (the force required to extrude the paste from the storage container to the mixer) was measured using a universal testing machine (manufactured by Shimadzu Corporation, product name "AG-I 100kN"). More specifically, the syringe container for the one-material type or the storage container for the two-material type was set vertically, and the crosshead equipped with the jig for the compressive strength test was lowered at 4 mm / min to discharge the paste while applying a load, and the maximum load at that time was taken as the discharge force. The measurement of the discharge force was performed at 25°C. In these tests, when the ejection force was 40N or less, it was judged to have passed because it was easy to eject and had excellent ejection properties, when it was 40N to 60N it was judged to have passed because it was possible to eject the product, although it could not be said to have excellent ejection properties, and when it exceeded 60N it was judged to have failed because it was difficult to eject the product.

[0128] <Fluoride ion release> In Examples 1 to 11 and Comparative Examples 1 to 4, each dental curable composition was filled into a mold having a diameter of 15 mm and a thickness of 1 mm, and the top and bottom were pressed with slide glasses via a PET film having a thickness of 50 μm. Next, both sides of the dental polymerizable composition filled in the mold were irradiated with light for 10 seconds at six points on each side using a dental visible light irradiator (product name "Pencure 2000", manufactured by Morita Corporation) to cure the dental polymerizable composition. In Examples 12 to 17 and Comparative Examples 5 to 7, the kneaded dental hardenable composition was placed in a mold having a diameter of 15 mm and a thickness of 1 mm, and the top and bottom were pressed with slide glasses via a PET film having a thickness of 50 μm. Then, the kneaded dental hardenable composition was left to stand in a thermostatic chamber at 37° C. for 1 hour to harden. The obtained cured product was removed from the mold and immersed in 4 ml of 0.2 M phosphate buffer (pH 7, 37°C). After immersion for 28 days, 2 mL of TISAB solution was added, and the amount of fluorine ions dissolved in the phosphate buffer at 25°C was quantified using a fluorine ion electrode (trade name "Orion (registered trademark)", manufactured by Thermo Fisher Scientific). In this test, if the fluorine ion concentration in the solution is 400 μg / g or more, an acid-resistant layer tends to be easily formed, and the fluorine ion release property is good.

[0129] <Calcium ion release> In Examples 1 to 11 and Comparative Examples 1 to 4, each dental curable composition was filled into a mold having a diameter of 15 mm and a thickness of 1 mm, and the top and bottom were pressed with slide glasses via a PET film having a thickness of 50 μm. Next, both sides of the dental polymerizable composition filled in the mold were irradiated with light for 10 seconds at six points on each side using a dental visible light irradiator (product name "Pencure 2000", manufactured by Morita Corporation) to cure the dental polymerizable composition. In Examples 12 to 17 and Comparative Examples 5 to 7, the kneaded dental hardenable composition was placed in a mold having a diameter of 15 mm and a thickness of 1 mm, and the top and bottom were pressed with slide glasses via a PET film having a thickness of 50 μm. Then, the kneaded dental hardenable composition was left to stand in a thermostatic chamber at 37° C. for 1 hour to harden. The obtained hardened product was removed from the mold and immersed in 5 mL of ion-exchanged water (37°C). After immersion for 28 days, 5 mL of KCl aqueous solution (15 g / L) was added, and the amount of calcium ions dissolved in the ion-exchanged water at 25°C was quantified using a calcium ion electrode (product name "8203-10C", manufactured by Horiba, Ltd.) in this test. If the calcium ion concentration in the solution is 200 μg / g or more, an acid-resistant layer tends to be formed easily, and calcium ion release properties are good.

[0130] <Flexural strength and flexural modulus> The evaluation was performed by bending test in accordance with ISO4049. Specifically, in Examples 1 to 11 and Comparative Examples 1 to 4, each dental curable composition was filled into a metal mold having a length of 2 mm, a thickness of 2 mm, and a length of 25 mm, and the top and bottom were pressed together with slide glass via a PET film having a thickness of 50 μm. Next, both sides of the dental polymerizable composition filled in the metal mold were irradiated with light for 10 seconds at five points on each side using a dental visible light irradiator (trade name "Pencure 2000", manufactured by Morita Corporation) to cure the dental polymerizable composition. In Examples 12 to 17 and Comparative Examples 5 to 7, the kneaded dental hardenable composition was placed in a mold measuring 2 mm in length, 2 mm in thickness, and 25 mm in length, and the top and bottom were pressed together with slide glasses via a 50 μm-thick PET film. Then, the mixture was left to stand in a thermostatic chamber at 37° C. for 1 hour to harden. The resulting cured product was subjected to a bending test at a crosshead speed of 2 mm / min using a universal testing machine (Shimadzu Corporation, "Autograph (registered trademark) AG-I 100 kN") to measure the bending strength and bending modulus. In this test, the bending strength is preferably 100 MPa or more, and more preferably 120 MPa or more. The flexural modulus is preferably 5.0 GPa or more, and more preferably 6.0 GPa or more.

[0131] <Adhesion durability> The labial surface of a bovine mandibular anterior tooth was polished with #80 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to form a flat dentin surface. The flat surface was further polished with #1000 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to form a smooth surface. A surgical tape measuring approximately 1 cm in length and width and having a circular hole with a diameter of 3.0 mm and a depth of 0.2 mm was attached to the obtained smooth surface to define the adhesion area. The tooth bonding primer prepared as described above was applied to the inside of the round hole using a brush, and after leaving it for 20 seconds, the surface was dried by blowing air over it until the applied tooth bonding primer had lost its fluidity. Next, in Examples 1 to 11 and Comparative Examples 1 to 4, each dental hardenable composition was filled into the round hole, and a 1 cm x 1 cm PET film was pressed against it, and then the dental hardenable composition was hardened by irradiating light for 10 seconds with a dental visible light irradiator (trade name "PenCure 2000", manufactured by Morita Corporation). Thereafter, the PET film was removed, and the film pressing surface was subjected to an alumina sandblasting treatment at a pressure of 2 MPa to roughen the surface of the hardened dental hardenable composition. One end face (circular cross section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm) was bonded to the roughened surface using a commercially available dental resin cement (trade name "Panavia (registered trademark) 21", manufactured by Kuraray Noritake Dental Co., Ltd.). In Examples 12 to 17 and Comparative Examples 5 to 7, a commercially available metal bonding primer (product name "Alloy Primer", manufactured by Kuraray Noritake Dental Co., Ltd.) was applied to one end face (circular cross section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm), the solvent was evaporated, and then each kneaded product of the dental hardenable composition was applied thereto. The stainless steel cylindrical rod was then stood upright and adhered so that the kneaded product of the dental hardenable composition was filled into the circular hole. After adhesion, the sample was left to stand at room temperature for 30 minutes and then immersed in distilled water. A total of 10 samples were prepared for the adhesion test, and all samples immersed in distilled water were stored in an incubator maintained at 37°C. After 24 hours, the samples were removed from the water and the tensile adhesive strength was measured using a universal testing machine (manufactured by Shimadzu Corporation). The tensile bond strength was measured with a crosshead speed set at 2 mm / min. The average value of the measurements of the five test pieces was taken as the tensile adhesive strength. The results are shown in Tables 1 to 3 below as "Adhesion after 24 hours." The remaining five test pieces bonded to dentin were subjected to a thermal cycle load of being alternately immersed in a 4°C water bath and a 60°C water bath for one minute each 4000 times, after which the tensile bond strength was measured. The bond durability was evaluated based on the tensile bond strength after this thermal cycle load. The results are shown in Tables 1 to 3 below as "Adhesive strength after TC4000". In this test, if the adhesive strength after 24 hours is 10 MPa or more and the adhesive strength after 4,000 thermal cycles is 8.0 MPa or more, the adhesive durability is excellent.

[0132] [Table 1]

[0133] [Table 2]

[0134] [Table 3]

[0135] In Tables 2 and 3, "mixture" means the total amount of the first material and the second material divided by two.

[0136] The results in Tables 1 and 2 show that the dental curable compositions of the examples containing components (A), (B), and (C) are excellent in ion release properties, flexural strength and flexural modulus, and adhesion durability. [Industrial Applicability]

[0137] The dental curable composition can be suitably used for dental composite resins, in particular, dental filling and restorative materials, dental cements, dental core building materials, and dental adhesives.

Claims

1. It contains a polyalkylenedi(meth)acrylate monomer (A), a polymerization initiator (B), and an ion-releasing compound (C), The aforementioned polyalkylenedi(meth)acrylate monomer (A) is subject to the following general formula [I] 【Chemistry 1】 (In the formula, R 1 R is a hydrocarbon group having 2 to 4 carbon atoms. 2 and R 3 Each of these is independently either a hydrogen atom or a methyl group, and n is an integer between 4 and 12. A dental hardening composition, which is a compound represented by [formula].

2. Furthermore, the dental curable composition according to claim 1, further containing a (meth)acrylic monomer (D) containing two or more (meth)acryloyloxy groups and one or more urethane bonds in one molecule.

3. Furthermore, the dental curable composition according to claim 2, further comprising the polyalkylenedi(meth)acrylic acid ester monomer (A) and a polymerizable monomer (E) other than the (meth)acrylic monomer (D).

4. Furthermore, the dental curable composition according to claim 1, further containing a polymerization accelerator (F).

5. Furthermore, the dental curable composition according to claim 1, further containing filler (G).

6. The dental curable composition according to claim 1, wherein the ion-releasing compound (C) contains at least one selected from the group consisting of fluoride ion-releasing compounds and calcium ion-releasing compounds.

7. The dental curable composition according to claim 2, wherein the (meth)acrylic monomer (D) does not contain a polymer skeleton.

8. The dental curable composition according to claim 2, wherein the (meth)acrylic monomer (D) is a compound with a molecular weight of 1000 or less.

9. The content of the polyalkylenedi(meth)acrylic acid ester monomer (A) is 1 to 90 parts by mass per 100 parts by mass of the total amount of polymerizable monomers, and The dental curable composition according to claim 2, wherein the content of the (meth)acrylic monomer (D) is 20 to 95 parts by mass per 100 parts by mass of the total amount of polymerizable monomers.

10. The dental curable composition according to claim 2, wherein the value expressed as the content of the (meth)acrylic monomer (D) / the content of the polyalkylenedi(meth)acrylic acid ester monomer (A) is 1 or more.

11. A dental filling and restorative material comprising a dental curable composition according to any one of claims 1 to 10.

12. A dental cement comprising a dental hardening composition according to any one of claims 1 to 10.

13. A dental core buildup material comprising a dental hardening composition according to any one of claims 1 to 10.

14. A dental adhesive comprising the dental curing composition described in any one of claims 1 to 10.

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