Polymerization accelerator, polymerization initiator, kit for preparing hardenable composition, hardenable composition, hardened product, and dental material

Abstract

The present invention provides a polymerization accelerator which contains a phosphonite compound.

Description

[Technical Field]

[0001] The present disclosure relates to a polymerization accelerator, a polymerization initiator, a kit for preparing a hardenable composition, a hardenable composition, a cured product, and a dental material. [Background technology]

[0002] In the field of dentistry, synthetic resin moldings are used to repair missing teeth. For example, hardenable compositions known as cements are used as tooth substitutes to repair large missing teeth. In recent years, the range of uses for cements has expanded.

[0003] For the polymerization of hardenable compositions for dental materials such as cement, a photopolymerization initiator, a chemical polymerization initiator, or the like can be used. For example, one common chemical polymerization initiator system is a redox polymerization initiator, which combines an oxidizing agent and a reducing agent. Known redox polymerization initiators include a polymerization initiator system that uses an organic peroxide as an oxidizing agent and an aromatic amine compound as a reducing agent.

[0004] Patent Document 1 discloses a redox initiator system containing sulfite. [Patent Document 1] International Publication No. 2017 / 100231 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the polymerization initiator described in Patent Document 1 leaves room for improvement in terms of the polymerizability of the monomer.

[0006] An object of one embodiment of the present disclosure is to provide a polymerization accelerator, a polymerization initiator, a kit for preparing a curable composition, a curable composition, a cured product, and a dental material that can satisfactorily improve the polymerizability of a monomer. [Means for solving the problem]

[0007] Specific means for solving the above problems include the following aspects. <1> A polymerization accelerator comprising a phosphonite compound. <2> The phosphonite compound includes a structure represented by the following general formula (X): <1> The polymerization accelerator according to claim 1.

[0008] [ka]

[0009] (In general formula (X), * indicates the bonding position to the carbon atom.) <3> The phosphonite compound includes a compound represented by the following general formula (Y): <1> or <2> The polymerization accelerator according to claim 1.

[0010] [ka]

[0011] (In general formula (Y), R B1 is an n-valent hydrocarbon group, and R B2 and R B3 are each independently a monovalent hydrocarbon group, and n is an integer of 1 or 2. <4> <1> ~ <3> 1. A polymerization initiator comprising the phosphonite compound according to any one of 1 to 8 above, an oxidizing agent, and a reducing agent. <5> a first agent containing a monomer (1); a second agent containing a monomer (2), At least one of the first agent and the second agent is <1> ~ <3> 1. A kit for preparing a curable composition, comprising the phosphonite compound according to any one of 1 to 8, an oxidizing agent, and a reducing agent, each of which independently comprises: <6> the oxidizing agent comprises an organic peroxide; The reducing agent includes an ascorbic acid and a transition metal compound. <5> A kit for preparing the curable composition described above. <7> the first agent contains the transition metal compound and the organic peroxide; The second agent contains the ascorbic acid and the phosphonite compound. <6> A kit for preparing the curable composition described above. <8> Either the monomer (1) in the first agent or the monomer (2) in the second agent contains an acidic group-containing monomer. <5> ~ <7> 10. A kit for preparing a curable composition according to any one of the above. <9> The monomer (1) in the first agent contains an acidic group-containing monomer, The second agent contains the ascorbic acid and the phosphonite compound. <6> or <7> A kit for preparing the curable composition described above. <10> The second agent contains the ascorbic acid and the phosphonite compound. <6> ~ <9> 10. A kit for preparing a curable composition according to any one of the above. <11> The first agent and the second agent contain a filler. <5> ~ <10> 10. A kit for preparing a curable composition according to any one of the above. <12> The total content of the phosphonite compound contained in the first agent and the second agent is 0.1% by mass to 1.5% by mass based on the total mass of the curable composition prepared. <5> ~ <11> 10. A kit for preparing a curable composition according to any one of the above. <13> <1> ~ <3> 1. A curable composition comprising the phosphonite compound according to any one of 1 to 8 above, an oxidizing agent, a reducing agent, and a monomer. <14> <13> A cured product of the curable composition described in 1. <15> <14> A dental material comprising the cured product according to claim 1. [Effects of the Invention]

[0012] According to one embodiment of the present disclosure, it is possible to provide a polymerization accelerator, a polymerization initiator, a kit for preparing a curable composition, a curable composition, a cured product, and a dental material that can satisfactorily improve the polymerizability of a monomer. DETAILED DESCRIPTION OF THE INVENTION

[0013] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, when there are multiple substances corresponding to each component, the amount of each component means the total amount of the multiple substances unless otherwise specified. In the present disclosure, "(meth)acrylic" means acrylic and methacrylic, and "(meth)acryloyl" means acryloyl and methacryloyl. In the present disclosure, "A or B" means at least one of A and B, and may include both A and B (for example, a mixture of A and B).

[0014] <Polymerization accelerator> The polymerization accelerator of the present disclosure contains a phosphonite compound. By using a polymerization accelerator containing a phosphonite compound, the polymerizability of the monomer can be improved. The polymerization accelerator of the present disclosure may contain one or more phosphonite compounds, or may contain two or more phosphonite compounds.

[0015] <Phosphonite compounds> The phosphonite compound may be any trivalent organic phosphorus compound in which a carbon atom is bonded to a phosphorus atom. The phosphonite compound contained in the polymerization accelerator of the present disclosure preferably has a structure represented by the following general formula (X):

[0016] [ka]

[0017] In general formula (X), * indicates the bonding position to a carbon atom. Three * are preferably bonding positions to carbon atoms contained in a hydrocarbon group, and more preferably bonding positions to carbon atoms contained in a benzene ring.

[0018] The phosphonite compound may contain one structure represented by general formula (X), or two or more structures represented by general formula (X). The phosphonite compound preferably contains two structures represented by general formula (X), and more preferably contains a skeleton in which two structures represented by general formula (X) are bonded via a divalent linking group (preferably a biphenyl structure).

[0019] The phosphonite compound contained in the polymerization accelerator of the present disclosure preferably includes a compound represented by the following general formula (Y).

[0020] [ka]

[0021] In general formula (Y), R B1 is an n-valent hydrocarbon group, and R B2 and R B3 are each independently a monovalent hydrocarbon group, and n is an integer of 1 or 2.

[0022] R B1 Examples of the n-valent hydrocarbon group in the formula include an n-valent aliphatic hydrocarbon group, an n-valent alicyclic hydrocarbon group, an n-valent aromatic hydrocarbon group, and a combination of two or more of these.

[0023] R B1 The monovalent hydrocarbon group in R is preferably an alkyl group, a phenyl group, a biphenyl group, or the like. B1 The hydrogen atoms of the phenyl group or biphenyl group in the formula (I) may be substituted with a substituent such as an alkyl group. R B1 The divalent hydrocarbon group in R is preferably an alkylene group, a phenylene group, or a biphenylene group such as a 4,4'-biphenylene group, a 4,3'-biphenylene group, or a 3,3'-biphenylene group.B1 The hydrogen atoms contained in the phenylene group or biphenylene group in the formula (I) may be substituted with a substituent such as an alkyl group.

[0024] R B2 and R B3 are each independently a monovalent hydrocarbon group, and are preferably an alkyl group, a phenyl group, or the like. B2 and R B3 The hydrogen atom contained in the phenyl group in the formula (I) may be substituted with an alkyl group such as a tert-butyl group or an n-butyl group.

[0025] n is an integer of 1 or 2, with 2 being preferred.

[0026] Specific examples of the phosphonite compound contained in the polymerization accelerator of the present disclosure include, for example, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene-diphosphonite, tetrakis(2,4-di-tert-butyl-5-methylphenyl)4,4'-biphenylene-diphosphonite, tetrakis(2,4-di-tert-butylphenyl)4,3'-biphenylene-diphosphonite, tetrakis(2,4-di-tert-butylphenyl)3,3'-biphenylene-diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene-diphosphonite, and tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene-diphosphonite. bis(2,4-di-tert-butylphenyl)-4,3'-biphenylene-diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene-diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, and the like.

[0027] The polymerization accelerator of the present disclosure may be a polymerization accelerator consisting solely of a phosphonite compound, or may be a polymerization accelerator consisting of a phosphonite compound and other polymerization accelerators, such as phosphite compounds, sulfite compounds, inorganic salts, and thiourea. When other polymerization accelerators are used, one type may be used alone, or two or more types may be used in combination.

[0028] Examples of phosphite compounds include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono(tridecyl) phosphite, and tris(2,4-di-tert-butylphenyl) phosphite.

[0029] Examples of sulfite compounds include ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethyl methyl sulfite, methyl-n-propyl sulfite, ethyl-n-propyl sulfite, di-n-propyl sulfite, diphenyl sulfite, methyl phenyl sulfite, ethyl sulfite, dibenzyl sulfite, benzyl methyl sulfite, and benzyl ethyl sulfite.

[0030] Examples of inorganic salts include sodium sulfite, calcium sulfite, potassium sulfite, potassium nitrate, potassium chloride, potassium sulfate, and sodium chloride.

[0031] Examples of thioureas include acetylthiourea, phenylthiourea, triethylthiourea, tetramethylthiourea, dimethylthiourea, and diphenylthiourea.

[0032] When the polymerization accelerator of the present disclosure is composed of a phosphonite compound and another polymerization accelerator, the content of the phosphonite compound may be 50% by mass to 99% by mass, 60% by mass to 98% by mass, or 70% by mass to 97% by mass, based on the total amount of the polymerization accelerator.

[0033] When the polymerization accelerator of the present disclosure is composed of a phosphonite compound and other polymerization accelerators, the content of the other polymerization accelerators may be 0.5% by mass to 30% by mass, 1% by mass to 20% by mass, or 1.5% by mass to 10% by mass, based on the total amount of the polymerization accelerator.

[0034] <Polymerization initiator> The polymerization initiator of the present disclosure includes the above-described phosphonite compound or the polymerization accelerator of the present disclosure, an oxidizing agent, and a reducing agent. The polymerization initiator of the present disclosure is a redox-based polymerization initiator that combines an oxidizing agent and a reducing agent.

[0035] The preferred embodiments of the phosphonite compound or polymerization accelerator contained in the polymerization initiator of the present disclosure are as described above. In the polymerization initiator of the present disclosure, the content of the phosphonite compound or the content of the polymerization accelerator is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the polymerization initiator.

[0036] <Oxidizing agent> The polymerization initiator of the present disclosure includes an oxidizing agent. The oxidizing agent is not particularly limited as long as it is an oxidizing agent that can be used in a redox-based polymerization initiator, and examples thereof include peroxides.

[0037] Peroxides include organic peroxides and inorganic peroxides, and the peroxides in the present disclosure preferably include organic peroxides.

[0038] (organic peroxide) The organic peroxide is not particularly limited and known organic peroxides can be used. Representative organic peroxides include hydroperoxides, peroxyesters, ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, and peroxydicarbonates. Among these, hydroperoxides are preferred because they have little fluctuation in the usable time even when the curable composition is provided in a packaged form and stored for a long period of time. One type of organic peroxide may be used alone, or multiple types may be used in combination.

[0039] More specifically, examples of the hydroperoxide include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and t-amyl hydroperoxide.

[0040] Any known peroxyester can be used without any limitations as long as it contains an acyl group on one side of a peroxy group (-OO- group) and a hydrocarbon group (or a group similar thereto) on the other side. Specific examples include α,α-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, and t-butyl peroxy-2-ethylhexanoate. Examples include 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, etc. These can be used alone or in appropriate combinations of two or more.

[0041] Examples of the ketone peroxide include methyl ethyl ketone peroxide, cyclohexanoperoxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, and acetylacetone peroxide.

[0042] Examples of peroxyketals include 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexanone, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclodecane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane.

[0043] Examples of dialkyl peroxides include α,α-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane-3.

[0044] Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, and benzoyl peroxides.

[0045] Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutyl) peroxydicarbonate.

[0046] (Inorganic peroxide) Examples of inorganic peroxides include peroxodisulfates and peroxodiphosphates, and among these, peroxodisulfates are preferred from the viewpoint of curability. Specific examples of peroxodisulfates include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate.

[0047] The peroxodisulfates may be used alone or in combination. Among the peroxodisulfates, sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate are preferred.

[0048] In the polymerization initiator of the present disclosure, the content of the oxidizing agent is preferably 20 parts by mass to 90 parts by mass, more preferably 30 parts by mass to 80 parts by mass, and even more preferably 40 parts by mass to 70 parts by mass, relative to 100 parts by mass of the polymerization initiator.

[0049] <Reducing agent> The polymerization initiator of the present disclosure includes a reducing agent. The reducing agent is not particularly limited as long as it is a reducing agent that can be used for a redox-based polymerization initiator, and examples thereof include ascorbic acids, sulfinic acids, amine compounds, and transition metal compounds.

[0050] (Ascorbic acids) Examples of the ascorbic acid reducing agent include ascorbic acid, ascorbic acid derivatives, salts thereof, etc. From the viewpoint of improving the adhesiveness of the resulting cured product, it is preferable to use an ascorbic acid derivative or a salt thereof.

[0051] Examples of salts of ascorbic acid include alkali metal salts of ascorbic acid and alkaline earth metal salts of ascorbic acid, and more specifically, examples thereof include sodium salts, potassium salts, magnesium salts, calcium salts, etc. of ascorbic acid.

[0052] Examples of ascorbic acid derivatives include compounds in which a portion of the structure of the ascorbic acid skeleton is substituted, such as compounds in which ascorbic acid has been subjected to the introduction of a substituent, oxidation, reduction, atom substitution, etc. The ascorbic acid derivative may be a compound in which at least one of the four hydroxyl groups contained in ascorbic acid has been substituted with another group.

[0053] The ascorbic acid derivative preferably has a structure in which at least one of the hydroxyl groups contained in ascorbic acid is substituted with an ether bond bonded to a carbon atom.

[0054] Examples of the salts of ascorbic acid derivatives include alkali metal salts of ascorbic acid derivatives and alkaline earth metal salts of ascorbic acid derivatives, and more specifically, sodium salts, potassium salts, magnesium salts, calcium salts of ascorbic acid derivatives, etc. Among these, calcium salts are preferred from the viewpoint of the balance between polymerizability and adhesiveness.

[0055] The ascorbic acid derivative or a salt thereof may contain a structure in which at least one of the four hydroxyl groups contained in ascorbic acid is substituted with an ether bond bonded to a carbon atom, and preferably contains a structure in which two of the four hydroxyl groups contained in ascorbic acid are substituted with ether bonds bonded to a carbon atom.

[0056] The ascorbic acid derivative preferably contains a structure represented by the following general formula (A).

[0057] [ka]

[0058] In general formula (A), * indicates the bonding position to the carbon atom. Two * in general formula (A) may be bonded to the same carbon atom to form a 1,3-dioxolane skeleton.

[0059] The ascorbic acid derivative preferably contains a compound represented by the following general formula (B).

[0060] [ka]

[0061] In general formula (B), R 1B and R 2B are each independently a hydrogen atom or a monovalent organic group. R 1B and R 2B At least one of the groups is preferably a monovalent organic group. R 1B and R 2B The monovalent organic group in the formula (I) is preferably an organic group having 1 to 12 carbon atoms, more preferably an organic group having 1 to 10 carbon atoms, and even more preferably an organic group having 3 to 10 carbon atoms.

[0062] In general formula (B), R 1B or R 2B is a hydrogen atom, and R 1B or R 2B The other may be a monovalent organic group having 1 to 10 carbon atoms.

[0063] R 1B and R 2B The monovalent organic group in may be an organic group containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like, or may be a hydrocarbon group to which an oxygen atom, a nitrogen atom, a sulfur atom, or the like is bonded, or may be a hydrocarbon group.

[0064] The salt of the ascorbic acid derivative may be a salt of a compound represented by general formula (B), or may be an alkali metal salt or alkaline earth metal salt of a compound represented by general formula (B). From the viewpoint of the balance between polymerizability and adhesiveness, a calcium salt of a compound represented by general formula (B) is preferred.

[0065] When the salt of the ascorbic acid derivative is a salt of a compound represented by general formula (B), R 1B and R 2B are preferably each independently a hydrogen atom or a monovalent organic group.1B or R 2B is a hydrogen atom, and R 1B or R 2B The other is a monovalent organic group having 1 to 10 carbon atoms, or R 1B and R 2B are preferably each independently a monovalent organic group having 1 to 10 carbon atoms. R 1B or R 2B is a hydrogen atom, and R 1B or R 2B and the other is a monovalent organic group having 1 to 10 carbon atoms, R 1B or R 2B The other is preferably a monovalent organic group having 1 to 5 carbon atoms, more preferably a monovalent organic group having 1 to 3 carbon atoms, further preferably a methyl group, ethyl group, propyl group or isopropyl group, and particularly preferably an isopropyl group. R 1B and R 2B are each independently a monovalent organic group having 1 to 10 carbon atoms, R 1B and R 2B are each independently preferably a monovalent organic group having 1 to 5 carbon atoms, more preferably a monovalent organic group having 1 to 3 carbon atoms, further preferably a methyl group, ethyl group, propyl group, or isopropyl group, and particularly preferably a methyl group.

[0066] An example of a method for producing an ascorbic acid derivative is a method in which ascorbic acid represented by the following general formula (C) is subjected to an acetalization reaction (see dashed line) with an aldehyde compound represented by the following general formula (D) or a ketone compound represented by the following general formula (E).

[0067] [ka]

[0068] R in the above general formula (D) is R in the above general formula (B). 1B or R 2B is the same as: The two R in the general formula (E) are the same as the R in the general formula (B) 1B and R 2B The two R's in the above general formula (E) may be the same or different. Examples of the aldehyde compound represented by the general formula (D) include butanal, isobutanal, hexanal, octanal, dodecanal, etc. Examples of the ketone compound represented by the general formula (E) include acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. These compounds may be used alone or in combination of two or more.

[0069] An example of a method for producing an alkali metal salt of an ascorbic acid derivative, which is a salt of the above-mentioned ascorbic acid derivative, is a method (alkali metalation reaction) in which an ascorbic acid derivative represented by the following general formula (B) is reacted with an alkali metal salt represented by the following general formula (F):

[0070] [ka]

[0071] In the general formula (F), X represents an alkali metal, and R represents, for example, a carbonate group or a hydroxyl group. Examples of the alkali metal salt represented by the general formula (F) include sodium hydroxide, sodium bicarbonate, sodium carbonate, calcium hydroxide, calcium carbonate, etc. These may be used alone or in combination of two or more.

[0072] The reaction conditions for the above-mentioned acetalization reaction and alkali metalation reaction may be appropriately adjusted.

[0073] (Sulfinic acids) Examples of sulfinic acids that serve as reducing agents include sulfinic acid compounds and salts thereof.

[0074] Examples of the sulfinic acid compound or a salt thereof include alkane sulfinic acids or a salt thereof, alicyclic sulfinic acids or a salt thereof, and aromatic sulfinic acids or a salt thereof. Examples of salts of sulfinic acid compounds include lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, strontium salts, iron salts, zinc salts, ammonium salts, tetramethylammonium salts, and tetraethylammonium salts.

[0075] Examples of alkanesulfinic acids include methanesulfinic acid. Examples of alicyclic sulfinic acids include cyclohexanesulfinic acid and cyclooctanesulfinic acid. Examples of aromatic sulfinic acids include benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalenesulfinic acid.

[0076] (amine compounds) Examples of the amine compound that serves as a reducing agent include aromatic amine compounds, aliphatic amine compounds, and heterocyclic amine compounds. From the viewpoint of improving the polymerizability, the amine compound preferably contains an aromatic amine compound. An aromatic amine compound contains an aromatic hydrocarbon group in its structure. The aromatic amine compounds of the present disclosure do not include heterocyclic aromatic compounds.

[0077] Examples of aromatic amine compounds include aromatic primary amine compounds such as aniline and toluidine; aromatic secondary amine compounds such as aromatic substituted amino acid compounds or salts thereof, typified by aromatic substituted glycines such as N-methylaniline, N-methyl-p-toluidine, N-phenylglycine (NPG), N-tolylglycine (NTG), and N,N-(3-methacryloyloxy-2-hydroxypropyl)phenylglycine (NPG-GMA), or alkali metal salts, alkaline earth metal salts, amine salts, and ammonium salts thereof; Aromatic tertiary amine compounds such as N,N-dimethylaniline (DMA), N,N-dibenzylaniline, N,N-dimethyl-p-toluidine (DMPT), N,N-diethyl-p-toluidine, N,N-di(2-hydroxyethyl)-p-toluidine (DEPT), N,N-dimethyl-p-ethylaniline, N,N-dimethyl-p-isopropylaniline, N,N-dimethyl-p-tert-butylaniline, N,N-dimethylanisidine, N,N-dimethylxylidine, N,N-dimethyl-3,5-di-t-butylaniline, N,N-dimethyl-p-chloroaniline, and N,N-dimethyl-p-fluoroaniline, or salts thereof Examples include:

[0078] The aliphatic amine compound is preferably an aliphatic amine compound containing at least one selected from the group consisting of primary, secondary, and tertiary amino groups, and more preferably an aliphatic amine compound containing only tertiary amino groups. As the heterocyclic amine compound, a heterocyclic amine compound containing at least one selected from the group consisting of primary, secondary, and tertiary amino groups is preferred, and a heterocyclic amine compound containing only tertiary amino groups is more preferred.

[0079] Examples of aliphatic amine compounds include EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), TTHA (triethylenetetraminehexaacetic acid), PDTA (1,3-propanediaminetetraacetic acid), DPTA-OH (1,3-diamino-2-hydroxypropanetetraacetic acid), HIDA (hydroxyethyliminodiacetic acid), DHEG (dihydroxyethylglycine), GEDTA (glycol ether diaminetetraacetic acid), CMGA (dialkoxymethyl ... Examples of suitable amines include ethylenediaminetetra(methylenephosphonic acid), EDDS ((S,S)-ethylenediaminedisuccinic acid) and EDTMP (ethylenediaminetetra(methylenephosphonic acid)), N,N-dimethyl-N',N'-bis(2-dimethylaminoethyl)ethylenediamine (Me6TREN), N,N'-dimethyl-1,2-phenylenediamine, 2-(methylamino)phenol, 3-(methylamino)-2-butanol, N,N'-bis(1,1-dimethylethyl)-1,2-ethanediamine, and N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA), or salts thereof.

[0080] Heterocyclic amine compounds include, for example, heterocyclic amine compounds that can function as monodentate, bidentate, or tridentate heterocyclic electron donor ligands. Specific examples thereof include heterocyclic amine compounds derived from unsubstituted or substituted heteroarenes such as furan, thiophene, pyrrole, pyridine, bipyridine, picollimine, γ-pyran, γ-thiopyran, phenanthroline, pyrimidine, bis-pyrimidine, pyrazine, indole, coumarin, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole, isothiazole, quinoline, biquinoline, isoquinoline, biisoquinoline, acridine, chroman, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine, bismidazole, and bisoxazoline, and salts thereof.

[0081] The aliphatic amine compound or heterocyclic amine compound is preferably N,N-dimethyl-N',N'-bis(2-dimethylaminoethyl)ethylenediamine, 2,2'-bipyridine, N-butyl-2-pyridylmethanimine, 4,4'-di-tert-butyl-2,2'-dipyridine, 4,4'-dimethyl-2,2'-dipyridine, 4,4'-dinonyl-2,2'-dipyridine, N-dodecyl-N-(2-pyridylmethylene)amine, 1,1,4,7,10,10-hexamethyl-triethylenetetramine, N-octadecyl-N-(2-pyridylmethylene)amine, N,N,N',N",N"-pentamethyl-diethylenetriamine, 1,4,8,11-tetracyclotetradecane, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, tris[2-(diethylamino)ethyl]amine or tris(2-methylpyridyl)amine, more preferably N,N-dimethyl-N',N'-bis(2-dimethylaminoethyl)ethylenediamine (Me6TREN).

[0082] (Transition metal compounds) Examples of the transition metal compound that serves as a reducing agent include copper compounds, vanadium compounds, molybdenum compounds, scandium compounds, titanium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, and nickel compounds. Among the above, the transition metal compound preferably contains at least one of a copper compound and a vanadium compound, and more preferably contains a copper compound.

[0083] Examples of copper compounds include copper carboxylates such as copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octoate, copper octenoate, copper naphthenate, copper methacrylate, and copper 4-cyclohexylbutyrate; β-diketone coppers such as copper acetylacetonate, copper trifluoroacetylacetonate, copper hexafluoroacetylacetonate, copper 2,2,6,6-tetramethyl-3,5-heptanedionato, and copper benzoylacetone; β-ketoester coppers such as copper acetoacetate; copper alkoxides such as copper methoxide, copper ethoxide, copper isopropoxide, copper 2-(2-butoxyethoxy)ethoxide, and copper 2-(2-methoxyethoxy)ethoxide; copper dithiocarbamates such as copper dimethyldithiocarbamate; and salts of copper with inorganic acids such as copper nitrate and copper chloride. Among these, copper carboxylate, copper β-diketone, and copper β-ketoester are preferred, and copper acetate and copper acetylacetone are more preferred, from the viewpoint of solubility in and reactivity with respect to the monomer.

[0084] Examples of vanadium compounds include vanadyl acetylacetonate, vanadium naphthenate (III), vanadyl stearate, vanadium benzoylacetonate, bis(maltolato)oxovanadium (IV), and oxobis(1-phenyl-1,3-butanedionate)vanadium (IV).

[0085] In the polymerization initiator of the present disclosure, the content of the reducing agent is preferably 10 parts by mass to 60 parts by mass, more preferably 15 parts by mass to 55 parts by mass, and even more preferably 20 parts by mass to 50 parts by mass, relative to 100 parts by mass of the polymerization initiator.

[0086] When the polymerization initiator of the present disclosure contains an ascorbic acid as a reducing agent, the content of the ascorbic acid in the polymerization initiator of the present disclosure is preferably 10 parts by mass to 60 parts by mass, more preferably 15 parts by mass to 55 parts by mass, and even more preferably 20 parts by mass to 50 parts by mass, relative to 100 parts by mass of the polymerization initiator. When the polymerization initiator of the present disclosure contains a transition metal compound as a reducing agent, the content of the transition metal compound in the polymerization initiator of the present disclosure is preferably 0.001 to 1.0 part by mass, more preferably 0.005 to 0.8 parts by mass, and even more preferably 0.01 to 0.7 parts by mass, relative to 100 parts by mass of the polymerization initiator.

[0087] <Curable composition preparation kit> The kit for preparing a curable composition of the present disclosure includes a first agent containing a monomer (A) and a second agent containing a monomer (B), and at least one of the first agent and the second agent independently contains the above-mentioned phosphonite compound or the polymerization accelerator, oxidizing agent, and reducing agent of the present disclosure.

[0088] <Monomer> In the kit for preparing a curable composition of the present disclosure, the first part contains the monomer (A) and the second part contains the monomer (B). Monomer (A) and monomer (B) may be the same monomer or different monomers. As the monomer (A) and the monomer (B), known monomers can be used. The monomer (A) and the monomer (B) may be monomers that do not contain an acidic group, or may be monomers that contain an acidic group (hereinafter also referred to as "acidic group-containing monomers"). The monomer (A) and the monomer (B) preferably contain a monomer that does not contain an acidic group.

[0089] The monomer is a monomer that undergoes a radical polymerization reaction due to the action of the aforementioned phosphonite compound or the polymerization accelerator, oxidizing agent, and reducing agent of the present disclosure to become a polymer. The monomer constituting the monomer in the present disclosure is not limited to one type, and may be two or more types. Monomers not containing an acidic group include (meth)acrylate monomers not containing an acidic group. (Meth)acrylate monomers not containing an acidic group include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional monomers.

[0090] In the present disclosure, the content of the monomers (i.e., the total amount of the monomer (A) and the monomer (B) in the curable composition to be prepared) is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 75% by mass, and even more preferably 30% by mass to 60% by mass, relative to the total mass of the curable composition to be prepared.

[0091] Examples of monofunctional monomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate. Among these, 2-hydroxyethyl methacrylate (HEMA) is preferred.

[0092] Examples of aromatic compound-based bifunctional monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, and 2,2-bis(4-(meth)acryloyloxypolypropoxyphenyl)propane. Among these, 2,2-bis[4-(3-(methacryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA") and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane are preferred.

[0093] Examples of aliphatic compound-based bifunctional monomers include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, 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, acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA), 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane, and the like. Among these, glycerol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), 1,6-hexanediol dimethacrylate (HexDMA), neopentyl glycol dimethacrylate (NPG), 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA), and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane are preferred.

[0094] Examples of tri- or higher functional monomers include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

[0095] The above-mentioned monomers may be blended either alone or in combination.

[0096] The amount of the above-mentioned monomer not containing an acidic group to be blended is preferably in the range of 10 parts by mass to 100 parts by mass, more preferably in the range of 20 parts by mass to 100 parts by mass, and even more preferably in the range of 50 parts by mass to 100 parts by mass, relative to 100 parts by mass of the total amount of the monomer components in the kit for preparing a curable composition of the present disclosure. Furthermore, when the monomer components in the curable composition preparation kit of the present disclosure include an acidic group-containing monomer described below, the amount of the monomer not containing an acidic group is preferably 10 parts by mass to 99 parts by mass, more preferably 30 parts by mass to 97 parts by mass, and even more preferably 50 parts by mass to 95 parts by mass, relative to 100 parts by mass of the total amount of the monomer components in the curable composition preparation kit of the present disclosure.

[0097] The monomer (A) and the monomer (B) preferably contain a (meth)acrylic monomer (C) having a molecular weight of 100 to 5,000. The molecular weight of the (meth)acrylic monomer (C) is more preferably 120 to 3,000, further preferably 150 to 2,000, and particularly preferably 200 to 1,000.

[0098] The content of the (meth)acrylic monomer (C) relative to the total content of the monomer (A) and the monomer (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0099] (Acidic group-containing monomer) In the kit for preparing a curable composition of the present disclosure, it is preferable that either the monomer (A) in the first part or the monomer (B) in the second part contains an acidic group-containing monomer. By including an acidic group-containing monomer in at least one of the first and second agents, for example, when the hardenable composition preparation kit of the present disclosure is used for dental purposes, it is possible to impart good tooth structure and high adhesion to dental prosthetic materials.

[0100] From the viewpoint of suppressing the reaction between the ascorbic acid or the phosphonite compound and the acidic group-containing monomer, it is preferred that the monomer (A) in the first agent contains an acidic group-containing monomer, and the second agent contains an ascorbic acid and a phosphonite compound; It is more preferable that the monomer (A) in the first agent contains an acidic group-containing monomer, and the second agent does not contain an acidic group-containing monomer, but contains an ascorbic acid and a phosphonite compound.

[0101] The acidic group-containing monomer has at least one acidic group such as a phosphoric acid group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, or a carboxylic acid group, and also has an acryloyl group, Examples include monomers containing at least one polymerizable group such as a methacryloyl group, a vinyl group, or a styrene group. The acidic group-containing monomer has affinity for the adherend and also has a demineralizing effect on the tooth structure.

[0102] Examples of the phosphate group-containing monomer include (meth)acryloyloxyalkyl dihydrogen phosphates such as 10-(meth)acryloyloxydecyl dihydrogen phosphate (MDP), 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)acryloyloxy Examples of the alkyl acrylate include bis[2-(meth)acryloyloxydecyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3-di(meth)acryloyloxypropyl dihydrogenphosphate, 2-(meth)acryloyloxyethylphenylhydrogenphosphate, 2-(meth)acryloyloxyethyl-2-bromoethylhydrogenphosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogenphosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0103] Examples of pyrophosphate group-containing monomers include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0104] Examples of the thiophosphate group-containing monomer include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0105] Examples of the phosphonic acid group-containing monomer include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0106] Examples of sulfonic acid group-containing monomers include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl(meth)acrylate.

[0107] Carboxylic acid group-containing monomers include monomers containing one carboxy group in the molecule and monomers containing multiple carboxy groups in the molecule.

[0108] Monomers containing one carboxy group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, and 2-(meth)acryloyloxybenzoic acid. Examples of the acryloyloxybenzoic acid include 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate, and acid halides thereof.

[0109] Examples of monomers containing multiple carboxy groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, Examples include 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate, dihydroxyethyl methacrylate trimethylhexyl dicarbamate, and acid anhydrides or acid halides thereof.

[0110] Among the above-mentioned acidic group-containing monomers, 10-(meth)acryloyloxydecyl dihydrogen phosphate (MDP), 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxyethyl trimellitate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, and dihydroxyethyl methacrylate trimethylhexyl dicarbamate are preferred in terms of their high adhesive strength to the adherend. The above-mentioned acidic group-containing monomers may be used alone or in combination of two or more kinds.

[0111] The amount of the acidic group-containing monomer blended is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the total amount of the monomer components in the kit for preparing a curable composition of the present disclosure. When the amount of the acidic group-containing monomer is 1 part by mass or more, it is easy to obtain high adhesion to various adherends. Furthermore, when the amount of the acidic group-containing monomer is 50 parts by mass or less, it is easy to maintain a balance between polymerizability and adhesiveness. Note that the total amount of the monomer components means the total amount of the acidic group-containing monomer and the above-mentioned monomer not containing an acidic group.

[0112] As the monomer in the present disclosure, for example, monomers described in known documents such as WO 2012 / 157566, WO 2015 / 015220, WO 2015 / 015221, and JP 2016-094482 A can be used.

[0113] In the kit for preparing a curable composition according to the present disclosure, at least one of the first and second parts independently contains the aforementioned phosphonite compound or the polymerization accelerator, oxidizing agent, and reducing agent according to the present disclosure. Preferred embodiments of the aforementioned phosphonite compound or the polymerization accelerator, oxidizing agent, and reducing agent according to the present disclosure used in the kit for preparing a curable composition are as described above.

[0114] In the kit for preparing a curable composition according to the present disclosure, from the viewpoint of improving polymerizability, the oxidizing agent preferably contains an organic peroxide, and the reducing agent preferably contains an ascorbic acid and a transition metal compound.

[0115] In the kit for preparing a curable composition of the present disclosure, from the viewpoint of storage stability, the first agent preferably contains a transition metal compound and an organic peroxide, and the second agent preferably contains an ascorbic acid and a phosphonite compound.

[0116] The total content of the phosphonite compounds contained in the first and second parts is preferably 0.1 to 5 mass%, more preferably 0.2 to 3 mass%, and even more preferably 0.3 to 1 mass%, relative to the total mass of the curable composition prepared.

[0117] The total content of the phosphonite compounds contained in the first and second parts is preferably 0.1 to 1.5 mass%, more preferably 0.1 to 1 mass%, and even more preferably 0.2 to 0.5 mass%, relative to the total mass of the curable composition prepared.

[0118] The total content of the oxidizing agent contained in the first and second agents is preferably 0.1% by mass to 10% by mass, more preferably 0.3% by mass to 5% by mass, and even more preferably 0.5% by mass to 3% by mass, relative to the total mass of the curable composition prepared.

[0119] The total content of the reducing agent contained in the first agent and the second agent is preferably 0.2 mass % to 5 mass %, more preferably 0.3 mass % to 2 mass %, and even more preferably 0.5 mass % to 1.5 mass %, relative to the total mass of the curable composition prepared.

[0120] The total content of ascorbic acid contained in the first and second agents is preferably 0.2% by mass to 5% by mass, more preferably 0.3% by mass to 2% by mass, and even more preferably 0.5% by mass to 1.5% by mass, relative to the total mass of the curable composition prepared. The total content of the transition metal compounds contained in the first and second agents is preferably 0.0001 mass% to 0.1 mass%, more preferably 0.0002 mass% to 0.05 mass%, and even more preferably 0.0003 mass% to 0.02 mass%, relative to the total mass of the curable composition prepared.

[0121] <Filler> In the kit for preparing a curable composition of the present disclosure, at least one of the first and second parts may contain a filler, and it is preferable that the first and second parts contain a filler. The filler may be blended alone or in combination of two or more types. Examples of the filler include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers.

[0122] Examples of inorganic fillers include silica; silica-based minerals such as kaolin, clay, mica, and mica; and ceramics and glasses based on silica and containing Al2O3, B2O3, TiO2, ZrO2, BaO, La2O3, SrO, ZnO, CaO, PO5, Li2O, Na2O, etc. As the glass, lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass are preferably used. Crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride are also preferably used. Specifically, in terms of adhesive strength and ease of handling, fine particle silica having a primary particle diameter of 0.001 μm to 0.1 μm is preferably used. Commercially available products include "Aerosil OX50," "Aerosil 50," "Aerosil 200," "Aerosil 380," "Aerosil R972," and "Aerosil 130" (all manufactured by Nippon Aerosil Co., Ltd.).

[0123] Examples of organic fillers include polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymers, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

[0124] Examples of composite fillers of inorganic and organic fillers include those in which inorganic fillers are dispersed in organic fillers, and inorganic / organic composite fillers in which inorganic fillers are coated with various polymers.

[0125] To improve curability, mechanical strength, and handleability, the filler may be surface-treated with a known surface treatment agent such as a silane coupling agent before use. Examples of surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

[0126] The amount of filler added is preferably in the range of 10% by mass to 80% by mass, more preferably in the range of 30% by mass to 80% by mass, and even more preferably in the range of 50% by mass to 75% by mass, based on the total mass of the curable composition of the present disclosure.

[0127] (non-conductive filler) In the kit for preparing a curable composition of the present disclosure, at least one of the first part and the second part preferably contains a non-conductive filler. Non-conductive fillers have a resistance of 1.00 x 10 -4 This means a filler of Ωm or more. The upper limit of the resistance value of the non-conductive filler is not particularly limited, but for example, it is 1.00×10 20 It may be Ωm. Examples of materials for the non-conductive filler include organic substances such as polyethylene, polystyrene, phenolic resin, epoxy resin, acrylic resin, and benzoguanamine resin; and inorganic substances such as silica (dimethyl silylated silica, etc.), silicates (borosilicate glass (barium borosilicate glass, etc.), aluminosilicate glass (boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, barium aluminosilicate glass, etc.)), ceramics, boron nitride, and barium nitride.

[0128] Among the above, silica and silicates are preferred as the material of the non-conductive filler, and dimethylsilyl silica and barium aluminosilicate are more preferred.

[0129] It is preferable that the first agent contains a non-conductive filler, and that the content of the non-conductive filler relative to the total mass of the first agent is 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. When the non-conductive filler is contained in the second agent, it is preferable that the second agent contains the non-conductive filler, and that the content of the non-conductive filler relative to the total mass of the second agent is 10 mass% or more, more preferably 20 mass% or more, and even more preferably 30 mass% or more. In the kit for preparing a curable composition of the present disclosure, when the non-conductive filler is contained in the first agent, the content of the non-conductive filler relative to the total mass of the first agent is preferably 10 mass% or more, and when the non-conductive filler is contained in the second agent, the content of the non-conductive filler relative to the total mass of the second agent is preferably 10 mass% or more.

[0130] <Additives> The curable composition of the present disclosure may contain additives such as a photopolymerization initiator, a stabilizer (polymerization inhibitor), a colorant, a fluorescent agent, and an ultraviolet absorber. As the photopolymerization initiator, known photopolymerization initiators can be used, and examples thereof include camphorquinone (CQ), ethyl dimethylaminobenzoate (EDB), and 2-butoxyethyl 4-(dimethylamino)benzoate (BEDB). In addition, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecylammonium chloride, and triclosan may be added. The curable composition of the present disclosure may contain known dyes and pigments.

[0131] The kit for preparing a hardenable composition of the present disclosure is preferably for use with dental materials. Dental materials include, but are not limited to, dental adhesives, dental filling materials, dental sealants (dental fissure sealants), abutment construction materials, denture base resins, denture base lining materials, crown prosthetic resins (hard crown resins), and dental self-polymerizing resins. The hardenable composition preparation kit of the present disclosure is particularly preferably used as a dental adhesive. Examples of dental adhesives include dental adhesive resin cements, orthodontic adhesives, adhesives for fixing loose teeth, adhesives for cavity application, and dental bonding materials, with dental adhesive resin cements being preferred. Examples of dental filling materials include dental composite resins (including dental self-adhesive composite resins), root canal filling materials, temporary sealing materials, and lining materials.

[0132] Kits for preparing hardenable compositions of the present disclosure may be used in dental treatment. For example, the dental treatment method of the present disclosure may include a step of mixing the first and second parts of the hardenable composition preparation kit of the present disclosure to obtain a hardenable composition, and a step of polymerizing the hardenable composition in the oral cavity to obtain a cured product. In this method, the step of mixing the first and second parts to obtain a hardenable composition may be performed either in the oral cavity or outside the oral cavity. When performed outside the oral cavity, the obtained hardenable composition may be applied to the oral cavity and polymerized in the oral cavity to obtain a hardened product. Such a method including a step of polymerizing in the oral cavity to obtain a hardened product is suitable, for example, when the hardenable composition preparation kit is used for dental adhesive resin cements, composite resins for filling and restoring, etc.

[0133] The dental treatment method of the present disclosure may include a step of polymerizing the hardenable composition of the present disclosure outside the oral cavity to obtain a cured product, and a step of applying the cured product into the oral cavity. The step of polymerizing the hardenable composition outside the oral cavity to obtain a cured product may be a step of polymerizing the hardenable composition in a casting mold to obtain a cured product. The cured product obtained outside the oral cavity may be processed as needed, and the processed cured product may be applied into the oral cavity. The method of polymerizing the hardened product outside the oral cavity to obtain a cured product is suitable, for example, when the cured product is used for CAD / CAM resin blocks, temporary crowns, artificial teeth, etc.

[0134] <Curable composition> The curable composition of the present disclosure contains the phosphonite compound or the polymerization accelerator of the present disclosure, an oxidizing agent, a reducing agent, and a monomer. When the curable composition of the present disclosure contains the above components, the polymerizability can be favorably improved. Specific examples and preferred embodiments of the monomer in the curable composition are the same as those of the monomer described above. The curable composition of the present disclosure preferably further comprises a non-conductive filler. Specific examples, preferred aspects, etc. of the non-conductive filler in the curable composition are the same as those of the non-conductive filler described above.

[0135] <Cured product> The cured product of the present disclosure is a cured product of the curable composition of the present disclosure, or a cured product obtained using the kit for preparing a curable composition of the present disclosure. The cured product of the present disclosure can be suitably used as a dental material. That is, the dental material of the present disclosure preferably contains the cured product of the present disclosure. [Example]

[0136] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples. The components used in this example are shown below.

[0137] <Polymerization accelerator> PPP: Tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene-diphosphonite TPP: Triphenyl phosphite PS: Di-n-propyl sulfite NaCl: Sodium chloride <Transition metal compounds> Cu(OAc)2monohydrate: Copper acetate monohydrate <Filler> GM27884: Schott GM27884, 1.5 μm, silane coupling agent treatment amount 2.3% R812: Evonik AEROSIL® R812 <Ascorbic acids> isoC4AAA: 3,4-dihydroxy-5-(2-isopropyl-1,3-dioxolan-4-yl)furan-2(5H)-one (see chemical formula below) <Monomers that do not contain acidic groups> 2-HBMA: 2-hydroxybutyl methacrylate TEGDMA: Triethylene glycol dimethacrylate UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate <Acidic group-containing monomer> MDP: 10-methacryloyloxydecyl dihydrogen phosphate <Organic peroxide> TAH: tert-amyl hydroperoxide <Photopolymerization initiator> BEDB: 2-butoxyethyl 4-(dimethylamino)benzoate CQ: Camphorquinone <Polymerization inhibitor> BHT: 2,6-di-tert-butyl-p-cresol

[0138] [ka]

[0139] <Synthesis Example 1 (Synthesis of isoC4AAA: 3,4-dihydroxy-5-(2-isopropyl-1,3-dioxolan-4-yl)furan-2(5H)-one)> Ascorbic acid (50.0 g, 284 mmol) and dimethylacetamide (105 mL) as a solvent were placed in an apparatus connected to a 300 mL eggplant-bottom flask and a Dimroth condenser, and the temperature was raised to 60° C., followed by stirring the solution uniformly. Next, isobutanal (20.2 g, 284 mmol) was added to the solution, and the solution was stirred uniformly. Furthermore, p-toluenesulfonic acid monohydrate (5.7 g, 28 mmol), an acid catalyst, was added, and the solution was stirred uniformly. After 20 hours, the reaction was stopped and the mixture was cooled to room temperature.

[0140] The resulting reaction product was then extracted. Specifically, an equal amount of distilled water was added to the reaction solution, followed by an equal amount of diethyl ether, and the mixture was extracted and washed in a separatory funnel. After repeating the above extraction three times, an equal amount of distilled water was added to the resulting organic layer, and the mixture was washed in a separatory funnel. After repeating the above washing three times, sodium sulfate was added to the resulting organic layer to dry it, and then it was concentrated under reduced pressure. The resulting crude product was washed with a hexane / ethyl acetate solvent and separated and purified by filtration.

[0141] As a result of the above, 3,4-dihydroxy-5-(2-isopropyl-1,3-dioxolan-4-yl)furan-2(5H)-one (16 g, 70 mmol, yield 24.6%) was obtained. 1 The assignments by H-NMR (CD3OD) are shown below. 1 H-NMR: δ0.39(td, 6H, J=4.5Hz,2.2Hz), 1.19-1.30(m, 1H), 3.39-3.79(m, 3H), 4.10-4.19(m, 2H)

[0142] The first and second agents of Example 1 and Comparative Examples 1 to 3 were prepared using each component as shown in Table 1. In Table 1, the numbers in the component column indicate the amount (parts by mass) of each component in the first or second agent.

[0143] <Polymerization evaluation> 100 mg of each of the first and second parts was weighed and mixed for 20 seconds. Approximately 100 mg of the mixed composition was quickly poured into an aluminum pan and measured using a NETZSCH Sirius DSC. The peak was analyzed, and the peak top (the time (minutes) at which the maximum peak value was obtained) and height (mW / mg) were calculated. The peak top (min) is an index of the polymerization rate, and the height (mW / mg) is an index of the degree of polymerization. The evaluation criteria for these are as follows: -Evaluation criteria for peak top (minutes)- A 2.0 or less B: Over 2.0 and under 2.4 C 2.4 or more and 3.0 or less D over 3.0 -Height (mW / mg) evaluation criteria- A 1.6 or higher B: Over 1.3 and under 1.6 C 0.6 or more and 1.3 or less D less than 0.6

[0144] [Table 1]

[0145] As shown in Table 1, Example 1, which used a phosphonite compound, had a better polymerizability rating than Comparative Examples 1 to 3.

[0146] The disclosure of Japanese Patent Application No. 2022-050803, filed on March 25, 2022, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A polymerization initiator comprising a polymerization accelerator containing a phosphonite compound, an oxidizing agent, and a reducing agent.

2. The polymerization initiator according to claim 1 , wherein the phosphonite compound comprises a structure represented by the following general formula (X): 【Chemistry 1】 (In general formula (X), * indicates the bonding position to the carbon atom.)

3. The polymerization initiator according to claim 1 or 2, wherein the phosphonite compound comprises a compound represented by the following general formula (Y): 【Chemistry 2】 (In general formula (Y), R Ｂ１ is an n-valent hydrocarbon group, and R Ｂ２ and R Ｂ３ are each independently a monovalent hydrocarbon group, and n is an integer of 1 or 2.

4. a first agent containing monomer (1); a second agent containing a monomer (2), At least one of the first part and the second part independently contains a phosphonite compound, an oxidizing agent, and a reducing agent.

5. the oxidizing agent comprises an organic peroxide; The kit for preparing a curable composition according to claim 4 , wherein the reducing agent comprises an ascorbic acid and a transition metal compound.

6. the first agent contains the transition metal compound and the organic peroxide; The kit for preparing a curable composition according to claim 5 , wherein the second agent comprises the ascorbic acid and the phosphonite compound.

7. The kit for preparing a curable composition according to any one of claims 4 to 6, wherein either the monomer (1) in the first agent or the monomer (2) in the second agent contains an acidic group-containing monomer.

8. The monomer (1) in the first agent includes an acidic group-containing monomer, The kit for preparing a curable composition according to claim 5 or 6, wherein the second agent comprises the ascorbic acid compound and the phosphonite compound.

9. The kit for preparing a curable composition according to claim 5 or 6, wherein the second agent comprises the ascorbic acid compound and the phosphonite compound.

10. The kit for preparing a curable composition according to any one of claims 4 to 6, wherein the first agent and the second agent contain a filler.

11. 7. The kit for preparing a curable composition according to claim 4, wherein a total content of the phosphonite compound contained in the first part and the second part is 0.1% by mass to 1.5% by mass, based on the total mass of the curable composition to be prepared.

12. A kit for preparing a curable composition according to any one of claims 4 to 6, wherein the phosphonite compound comprises a compound represented by the following general formula (Y): 【Transformation 3】 (In general formula (Y), R B1 represents an n-valent hydrocarbon group, R B2 and R B3 each independently represent a monovalent hydrocarbon group, and n represents an integer of 1 or 2.)

13. A curable composition comprising the polymerization initiator according to claim 1 or 2 and a monomer.

14. A cured product of the curable composition according to claim 13.

15. A dental material comprising the cured product according to claim 14.

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