Ascorbic acid derivative, additive for polymerization initiation, polymerization initiator, kit for preparing curable composition, curable composition, cured product, and dental material

Abstract

Provided is an ascorbic acid derivative which is an ascorbic acid compound or a salt thereof including a structure in which a hydrogen atom in at least one of the hydroxyl groups contained in the ascorbic acid is substituted with a silicon atom.

Description

Ascorbic acid derivative, polymerization initiation additive, polymerization initiator, kit for preparing hardenable composition, hardenable composition, hardened product, and dental material

[0001] The present disclosure relates to an ascorbic acid derivative, a polymerization initiation additive, a polymerization initiator, a kit for preparing a hardenable composition, a hardenable composition, a cured product, and a dental material.

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

[0004] Patent Document 1 discloses a redox initiator system containing ascorbic acid or an ascorbic acid ester, a transition metal component, and an organic peroxide.

[0005] Patent Document 1: International Publication No. 2016 / 007453

[0006] However, the curable composition containing ascorbic acid or an ascorbic acid ester as described in Patent Document 1 leaves room for improvement in terms of adhesiveness.

[0007] The problem to be solved by one embodiment of the present disclosure is to provide: an ascorbic acid derivative, a polymerization initiation additive, and a polymerization initiator that can improve the adhesiveness of a curable composition when used as components in the curable composition; a kit for preparing a curable composition that can prepare a curable composition with excellent adhesiveness; a curable composition with excellent adhesiveness; a cured product of the curable composition; and a dental material that includes the cured product.

[0008] Specific means for solving the above problems include the following aspects: <1> An ascorbic acid derivative, which is an ascorbic acid compound or a salt thereof, which has a structure in which a hydrogen atom in at least one of hydroxyl groups contained in ascorbic acid is replaced with a silicon atom. <2> The ascorbic acid derivative according to <1>, wherein the ascorbic acid compound has a structure represented by the following formula (A):

[0009]

[0010] In formula (A), A １１ and A １２ is a group represented by formula (A1), and A １１ and A １２ The other is a hydrogen atom or a group represented by formula (A1): In formula (A1), all four *s indicate bonding positions.

[0011] <3> The ascorbic acid derivative according to <1> or <2>, wherein the ascorbic acid compound is a compound represented by the following formula (B1) or the following formula (B2):

[0012]

[0013] In formula (B1), X １ and X ２ is a group represented by formula (X), and X １ and X ２ The other is a hydrogen atom or a group represented by formula (X). When two groups represented by formula (X) are present in formula (B1), the two groups represented by formula (X) may be the same or different. １ ~R ３ are each independently a monovalent organic group, and * represents a bonding position. ４ ~R ７ are each independently a monovalent organic group.

[0014] <4> A polymerization initiator additive containing the ascorbic acid derivative according to any one of <1> to <3>. <5> A polymerization initiator containing the ascorbic acid derivative according to any one of <1> to <3>, a transition metal compound, and an organic peroxide. <6> A kit for preparing a curable composition, comprising: a first agent containing a monomer (A); and a second agent containing a monomer (B), wherein the total components of the first agent and the second agent contain the ascorbic acid derivative, transition metal compound, and organic peroxide according to any one of <1> to <3>. <7> The kit for preparing a curable composition according to <6>, wherein the first agent contains the transition metal compound and the organic peroxide, and the second agent contains the ascorbic acid derivative. <8> The kit for preparing a curable composition according to <6> or <7>, wherein at least one of the monomer (A) in the first agent and the monomer (B) in the second agent contains an acidic group-containing monomer. <9> The curable composition preparation kit according to any one of <6> to <8>, wherein the monomer (A) in the first part contains an acidic group-containing monomer, and the second part contains the ascorbic acid derivative. <10> The curable composition preparation kit according to any one of <6> to <9>, wherein at least one of the first part and the second part contains a polymerization accelerator (1) that is at least one selected from the group consisting of a phosphonite compound, a phosphite compound, and a sulfite compound. <11> The curable composition preparation kit according to <10>, wherein the second part contains the ascorbic acid derivative and the polymerization accelerator (1). <12> The curable composition preparation kit according to any one of <6> to <11>, wherein at least one of the first part and the second part contains a filler. <13> The kit for preparing a hardenable composition according to any one of <6> to <12>, wherein the total content of the ascorbic acid derivative in the first agent and the second agent is 0.1% by mass to 5% by mass, based on the total mass of the hardenable composition to be prepared. <14> The kit for preparing a hardenable composition according to any one of <6> to <13>, which is used for preparing a hardenable composition for a dental material. <15> A hardenable composition comprising the ascorbic acid derivative according to any one of <1> to <3>, a transition metal compound, an organic peroxide, and a monomer.<16> A cured product of the hardenable composition according to <15>. <17> A dental material comprising the cured product according to <16>.

[0015] According to one embodiment of the present disclosure, there are provided: an ascorbic acid derivative, a polymerization initiation additive, and a polymerization initiator, which can improve the adhesiveness of a hardenable composition when used as components in the hardenable composition; a kit for preparing a hardenable composition, which can prepare a hardenable composition with excellent adhesiveness; a hardenable composition with excellent adhesiveness; a cured product of the hardenable composition; and a dental material including the cured product.

[0016] 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 multiple substances corresponding to each component are present, the amount of each component refers to the total amount of multiple substances unless otherwise specified. In the present disclosure, "(meth)acrylic" means acrylic and methacrylic, and "(meth)acryloyl" means acryloyl and methacryloyl.

[0017] <<Ascorbic Acid Derivative>> The ascorbic acid derivative (hereinafter also referred to as a specific ascorbic acid derivative) of the present disclosure is an ascorbic acid compound (hereinafter also referred to as a specific ascorbic acid compound) containing a structure in which the hydrogen atom of at least one of the hydroxyl groups contained in ascorbic acid is replaced with a silicon atom, or a salt of the specific ascorbic acid compound.

[0018] The specific ascorbic acid derivative is a compound that can improve the adhesiveness of a curable composition when used as a component in the curable composition. For example, the specific ascorbic acid derivative is superior in the effect of improving the adhesiveness of a curable composition compared to ascorbic acid (AA in Comparative Example 1 described later), ascorbic acid derivatives other than the specific ascorbic acid derivative (AS6P in Comparative Example 2 described later), and silyl compounds other than the specific ascorbic acid derivative (MPTS in Comparative Example 3 described later).

[0019] The curable composition in which the ascorbic acid derivative of the present disclosure is used is not limited to a one-component curable composition, but may be a multi-component (e.g., two-component) curable composition. An example of a multi-component (e.g., two-component) curable composition is a curable composition preparation kit containing a first component and a second component, as described below. The curable composition preparation kit is a kit for preparing a curable composition by mixing the first component and the second component. In this case, one or both of the first component and the second component contain a specific ascorbic acid derivative.

[0020] The specific ascorbic acid derivative may be an additive (polymerization initiation additive) added to a polymerization initiator, or may be a compound used as a polymerization initiator in combination with other components (e.g., a transition metal compound, an organic peroxide, etc.).

[0021] As described above, the specific ascorbic acid derivative is a specific ascorbic acid compound or a salt of a specific ascorbic acid compound.

[0022] The specific ascorbic acid compound is an ascorbic acid compound having a structure in which a hydrogen atom in at least one of the hydroxyl groups contained in ascorbic acid is replaced with a silicon atom. The specific ascorbic acid compound may have a ring structure.

[0023] The molecular weight of the specific ascorbic acid derivative (i.e., the specific ascorbic acid compound or the salt of the specific ascorbic acid compound) is preferably 2,000 or less, more preferably 230 to 2,000, even more preferably 260 to 1,500, and still more preferably 300 to 1,000.

[0024] The molecular weight of the specific ascorbic acid compound is preferably 1,000 or less, more preferably 230 to 1,000, more preferably 260 to 1,000, and even more preferably 300 to 1,000.

[0025] Examples of the salt of the specific ascorbic acid compound include alkali metal salts and alkaline earth metal salts, more specifically sodium salts, potassium salts, magnesium salts, and calcium salts. As the salt of the specific ascorbic acid compound, calcium salts are preferred from the viewpoint of the aforementioned effect of improving adhesiveness.

[0026] The specific ascorbic acid compound preferably contains a structure represented by the following formula (A):

[0027]

[0028] In formula (A), A １１ and A １２ is a group represented by formula (A1), and A １１ and A １２ The other is a hydrogen atom or a group represented by formula (A1): In formula (A1), all four *s indicate bonding positions.

[0029] In the structure represented by formula (A), A １１ and A １２ may be bonded directly or via another atomic group to form a ring structure.

[0030] The specific ascorbic acid compound is preferably a compound represented by the following formula (B1) or (B2), and is preferably a compound represented by the following formula (B1) in that it can further suppress coloration of the cured product.

[0031] In formula (B1), X １ and X ２ is a group represented by formula (X), and X １ and X ２ The other is a hydrogen atom or a group represented by formula (X). When two groups represented by formula (X) are present in formula (B1), the two groups represented by formula (X) may be the same or different.１ ~R ３ are each independently a monovalent organic group, and * represents a bonding position. ４ ~R ７ are each independently a monovalent organic group.

[0032] In formula (X), R １ ~R ３ The monovalent organic group represented by the formula (I) is preferably a hydrocarbon group, more preferably an alkyl group, an aryl group, or an aralkyl group, even more preferably an alkyl group or an aryl group, and even more preferably an alkyl group.

[0033] In formula (X), R １ ~R ３ The monovalent organic group represented by the formula (I) preferably has 1 to 30 carbon atoms, more preferably 2 to 26 carbon atoms, and even more preferably 12 to 24 carbon atoms.

[0034] In formula (X), R １ ~R ３ More preferred monovalent organic groups represented by the formula (I) are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, and tetracosyl groups.

[0035] In formula (B2), R ４ ~R ７ A preferred embodiment of the monovalent organic group represented by formula (X) is １ ~R ３ The preferred embodiments are the same as those of the monovalent organic group represented by the following formula:

[0036] Specific examples of the specific ascorbic acid derivatives (i.e., specific ascorbic acid compounds or salts of specific ascorbic acid compounds) are as shown in the Examples below. Specific examples of the specific ascorbic acid compounds, in addition to those shown in the Examples below, include the following compound groups, and specific examples of salts of the specific ascorbic acid compounds include alkaline earth metal salts (e.g., Ca salts) of each of the following compound groups.

[0037]

[0038] <Polymerization Initiating Additive> The polymerization initiating additive of the present disclosure includes the ascorbic acid derivative of the present disclosure (i.e., the specific ascorbic acid derivative described above). A combination of the polymerization initiating additive of the present disclosure and other components (e.g., a transition metal compound, an organic peroxide, etc.) can be used as a polymerization initiator.

[0039] The polymerization initiator additive of the present disclosure may be an additive consisting solely of the ascorbic acid derivative of the present disclosure, or may be an additive consisting of the ascorbic acid derivative of the present disclosure and other components.

[0040] <Polymerization Initiator> The polymerization initiator of the present disclosure contains the ascorbic acid derivative of the present disclosure, a transition metal compound, and an organic peroxide.

[0041] In the polymerization initiator of the present disclosure, the content of the ascorbic acid derivative is preferably 10 parts by mass to 70 parts by mass, more preferably 15 parts by mass to 65 parts by mass, and even more preferably 20 parts by mass to 60 parts by mass, relative to 100 parts by mass of the polymerization initiator.

[0042] <Transition Metal Compound> The polymerization initiator of the present disclosure contains a transition metal compound. As the transition metal compound, a compound soluble in the monomer components in the curable composition preparation kit described below is preferred.

[0043] Examples of the transition metal compound include copper compounds, vanadium compounds, molybdenum compounds, scandium compounds, titanium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, etc. 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.

[0044] 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 acetylacetone, copper trifluoroacetylacetone, copper hexafluoroacetylacetone, 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; copper salts of copper and inorganic acids such as copper nitrate and copper chloride. These may be used alone or in combination of two or more. 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 the monomer.

[0045] Examples of vanadium compounds include vanadyl acetylacetonate, vanadium naphthenate (III), vanadyl stearate, vanadium benzoylacetonate, bis(maltolato)oxovanadium (IV), and oxobis(1-phenyl-1,3-butanedionato)vanadium (IV).

[0046] In the polymerization initiator of the present disclosure, the content of the transition metal compound is preferably 0.1 parts by mass to 1.5 parts by mass, more preferably 0.2 parts by mass to 1 part by mass, and even more preferably 0.3 parts by mass to 1 part by mass, relative to 100 parts by mass of the polymerization initiator.

[0047] <Organic Peroxide> The polymerization initiator of the present disclosure includes an 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.

[0048] 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.

[0049] Any 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 peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 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-toluoyl benzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, etc. These can be used alone or in appropriate combinations of two or more.

[0050] Examples of the ketone peroxide include methyl ethyl ketone peroxide, cyclohexanoperoxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, and acetylacetone peroxide.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] In the polymerization initiator of the present disclosure, the content of the organic peroxide is preferably 20 parts by mass to 90 parts by mass, more preferably 30 parts by mass to 85 parts by mass, and even more preferably 40 parts by mass to 80 parts by mass, relative to 100 parts by mass of the polymerization initiator.

[0056] <Kit for Preparing Curable Composition> The kit for preparing a curable composition according to the present disclosure includes: a first agent containing a monomer (A); and a second agent containing a monomer (B), wherein the combined components of the first agent and the second agent contain the ascorbic acid derivative, transition metal compound, and organic peroxide according to the present disclosure.

[0057] Here, "the total components of the first agent and the second agent contain the ascorbic acid derivative, transition metal compound, and organic peroxide of the present disclosure" means that the total components of all the components of the first agent and all the components of the second agent combined (note: this does not mean that the first agent and the second agent are actually mixed) contain the ascorbic acid derivative, transition metal compound, and organic peroxide of the present disclosure.

[0058] By mixing the first and second parts of the curable composition preparation kit of the present disclosure, a curable composition of the present disclosure, described below, containing the ascorbic acid derivative, transition metal compound, organic peroxide, and monomer of the present disclosure, can be prepared. In other words, the curable composition preparation kit of the present disclosure is a multi-part curable composition containing the first and second parts. When using the curable composition preparation kit of the present disclosure, the first and second parts are mixed to prepare the curable composition, for example, at the stage when the curable composition is used as an adhesive composition or immediately before that stage. That is, the first and second parts are kept separate prior to use. This can prevent unintended curing of the curable composition (specifically, unintended curing due to a reaction between the ascorbic acid derivative and the transition metal compound and / or organic peroxide).

[0059] From the viewpoint of further suppressing the reaction between the ascorbic acid derivative and the transition metal compound and / or organic peroxide, it is preferable that the first agent contains a transition metal compound and an organic peroxide, and the second agent contains an ascorbic acid derivative.

[0060] The preferred range of the molecular weight of the ascorbic acid derivative is as described above (eg, 260 to 500).

[0061] <Monomer> In the kit for preparing a curable composition according to the present disclosure, the first part contains a monomer (A), and the second part contains a monomer (B). The monomer (A) and the monomer (B) may be the same monomer or different monomers. Known monomers can be used as the monomer (A) and the monomer (B). 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"). It is preferable that the monomer (A) and the monomer (B) contain a monomer that does not contain an acidic group.

[0062] The monomer is a monomer that undergoes a radical polymerization reaction due to the action of the ascorbic acid derivative, transition metal compound, and organic peroxide of the present disclosure to form a polymer. The monomer constituting the monomer in the present disclosure is not limited to one type, and may be two or more types. Examples of the monomer that does not contain an acidic group include a (meth)acrylate monomer that does not contain an acidic group. Examples of the (meth)acrylate monomer that does not contain an acidic group include a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher functional monomer.

[0063] 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.

[0064] 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.

[0065] 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. Of these, 2,2-bis[4-(3-(methacryloyloxy)-2-hydroxypropoxyphenyl)propane (commonly known as "Bis-GMA") and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane are preferred.

[0066] 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, and 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.

[0067] 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, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0068] The above-mentioned monomers may be blended either individually or in combination.

[0069] The amount of the above-mentioned monomer not containing an acidic group is preferably in the range of 10 parts by mass to 100 parts by mass, more preferably 20 parts by mass to 100 parts by mass, and even more preferably 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 curable composition preparation kit 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.

[0070] Monomer (A) and monomer (B) preferably contain a (meth)acrylic monomer (C) having a molecular weight of 100 to 5000. The molecular weight of the (meth)acrylic monomer (C) is more preferably 120 to 3000, even more preferably 150 to 2000, and particularly preferably 200 to 1000.

[0071] 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.

[0072] In the kit for preparing a curable composition according to the present disclosure, at least one of the monomer (A) in the first agent and the monomer (B) in the second agent preferably contains an acidic group-containing monomer. When at least one of the first agent and the second agent contains an acidic group-containing monomer, for example, when the kit for preparing a curable composition according to the present disclosure is used for dental purposes, good tooth structure and high adhesion to dental prosthetic materials can be imparted.

[0073] From the viewpoint of suppressing the reaction between the ascorbic acid derivative and the acidic group-containing monomer, it is preferable that the monomer (A) in the first agent contains an acidic group-containing monomer and the second agent contains an ascorbic acid derivative, and 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 and contains an ascorbic acid derivative.

[0074] Examples of the acidic group-containing monomer include monomers having at least one acidic group such as a phosphate group, pyrophosphate group, thiophosphate group, phosphonate group, sulfonic acid group, or carboxylic acid group, and at least one polymerizable group such as an acryloyl group, methacryloyl group, vinyl group, or styrene group. The acidic group-containing monomer has affinity for the adherend and also has a demineralizing effect on tooth structure.

[0075] 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 2-(meth)acryloyloxyethylphenyl]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.

[0076] 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.

[0077] Examples of thiophosphate group-containing monomers include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0078] Examples of phosphonic acid group-containing monomers include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0079] Examples of sulfonic acid group-containing monomers include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl(meth)acrylate.

[0080] Carboxylic acid group-containing monomers include monomers containing one carboxy group in the molecule and monomers containing multiple carboxy groups in the molecule.

[0081] Examples of 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.

[0082] 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.

[0083] 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 adherends. The above-mentioned acidic group-containing monomers may be used alone or in combination of two or more types.

[0084] The amount of the acidic group-containing monomer 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 curable composition preparation kit 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 combined amount of the acidic group-containing monomer and the above-mentioned monomer not containing an acidic group.

[0085] 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.

[0086] From the viewpoint of adhesiveness, the total content of the ascorbic acid derivatives contained in the first agent and the second agent is preferably 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 3% by mass, and even more preferably 0.5% by mass to 2% by mass, relative to the total mass of the curable composition prepared.

[0087] From the viewpoint of curability, the total content of the transition metal compounds contained in the first agent and the second agent is preferably 0.00005 parts by mass to 0.1 parts by mass, more preferably 0.0001 parts by mass to 0.05 parts by mass, and even more preferably 0.001 parts by mass to 0.03 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.

[0088] From the viewpoint of curability, the total content of the organic peroxides contained in the first agent and the second agent is preferably 0.01 parts by mass to 6 parts by mass, more preferably 0.01 parts by mass to 4 parts by mass, and even more preferably 0.05 parts by mass to 3 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.

[0089] In the kit for preparing a curable composition according to the present disclosure, at least one of the first agent and the second agent may contain a polymerization accelerator (1) which is at least one selected from the group consisting of a phosphonite compound, a phosphite compound, and a sulfite compound.

[0090] From the viewpoint that the polymerization accelerator (1) can function as a stabilizer for the ascorbic acid derivative, it is preferable that the second agent contains an ascorbic acid derivative and a polymerization accelerator (1).

[0091] <Phosphonite Compound> 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 (1) of the present disclosure preferably has a structure represented by the following formula (I):

[0092]

[0093] In formula (I), * 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.

[0094] The phosphonite compound may contain one structure represented by formula (I), or two or more structures represented by formula (I). The phosphonite compound preferably contains two structures represented by formula (I), and more preferably contains a structure in which two structures represented by formula (I) are bonded via a divalent linking group (preferably a biphenyl structure).

[0095] The phosphonite compound contained in the polymerization accelerator (1) of the present disclosure preferably includes a compound represented by the following formula (II):

[0096]

[0097] In formula (II), 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.

[0098] R Ｂ１Examples of the n-valent hydrocarbon group in the formula (I) 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.

[0099] 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 R may be substituted with a substituent such as an alkyl group. 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.

[0100] R Ｂ２ and R Ｂ３ are each independently a monovalent hydrocarbon group, and an alkyl group, a phenyl group, or the like is preferred. 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.

[0101] n is an integer of 1 or 2, with 2 being preferred.

[0102] Specific examples of the phosphonite compound contained in the polymerization accelerator (1) of the present disclosure include, for example, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene-di-phosphonite, tetrakis(2,4-di-tert-butyl-5-methylphenyl)4,4′-biphenylene-di-phosphonite, tetrakis(2,4-di-tert-butylphenyl)4,3′-biphenylene-di-phosphonite, tetrakis(2,4-di-tert-butylphenyl)3,3′-biphenylene-di-phosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4′-biphenylene-di-phosphonite, tetrakis(2,6-di-t bis(2,4-di-tert-butylphenyl)-4,3'-biphenylene-di-phosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene-di-phosphonite, 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.

[0103] Examples of the phosphite compound 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.

[0104] 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.

[0105] From the viewpoint of curability, the total content of the polymerization accelerator (1) contained in the first agent and the second agent is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass, relative to 100 parts by mass of the total amount of the first agent and the second agent.

[0106] In the kit for preparing a curable composition according to the present disclosure, at least one of the first and second parts may contain a polymerization accelerator (2) other than the polymerization accelerator (1). The polymerization accelerator (2) according to the present disclosure is not particularly limited, and examples thereof include inorganic salts and thiourea.

[0107] Examples of inorganic salts include sodium sulfite, calcium sulfite, potassium sulfite, potassium nitrate, potassium chloride, potassium sulfate, and sodium chloride.

[0108] Examples of thioureas include acetylthiourea, phenylthiourea, triethylthiourea, tetramethylthiourea, dimethylthiourea, and diphenylthiourea.

[0109] From the viewpoint of curability, the total content of the polymerization accelerator (2) contained in the first agent and the second agent is preferably 0.0001 parts by mass to 1 part by mass, and more preferably 0.001 parts by mass to 0.1 parts by mass, relative to 100 parts by mass of the total amount of the first agent and the second agent.

[0110] From the viewpoint of curability, the total content of the inorganic salts contained in the first and second agents is preferably 0.0001 to 0.1 parts by mass, and more preferably 0.001 to 0.01 parts by mass, relative to 100 parts by mass of the total amount of the first and second agents.

[0111] From the viewpoint of curability, the total content of thiourea contained in the first agent and the second agent is preferably 0.001 part by mass to 1.0 part by mass, and more preferably 0.01 part by mass to 0.1 part by mass, relative to 100 parts by mass of the total amount of the first agent and the second agent.

[0112] <Filler> In the kit for preparing a curable composition according to the present disclosure, at least one of the first and second agents may contain a filler, and it is preferable that the first and second agents contain a filler. The filler may be a single type or a combination of multiple types. Examples of the filler include inorganic fillers, organic fillers, and composite fillers of inorganic and organic fillers.

[0113] Examples of inorganic fillers include silica; silica-based minerals such as kaolin, clay, mica, and mica; silica-based Al fillers; ２ O ３ , B ２ O ３ , TiO ２ , ZrO ２ , BaO, La ２ O ３ , SrO, ZnO, CaO, P ２ O ５ , Li ２ O, Na ２Examples of suitable glass include ceramics and glasses containing 0 and the like. Suitable glass materials include lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass. Suitable materials include 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. Specifically, in terms of adhesive strength and ease of handling, finely divided silica particles having a primary particle size of 0.001 μm to 0.1 μm are 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.).

[0114] Examples of organic fillers include polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymers, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

[0115] 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.

[0116] To improve curability, mechanical strength, and handleability, the filler may be surface-treated in advance with a known surface treatment agent such as a silane coupling agent. Examples of surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

[0117] The total content of the filler contained in the first agent and the second agent 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, relative to the total mass of the curable composition to be prepared.

[0118] (Non-conductive filler) In the kit for preparing a curable composition according to the present disclosure, at least one of the first and second parts preferably contains a non-conductive filler. －４ The upper limit of the resistance value of the non-conductive filler is not particularly limited, and is, for example, 1.00 × 10 ２０ 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.

[0119] 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.

[0120] Preferably, the first agent contains a non-conductive filler, and 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, the second agent contains a non-conductive filler, and the content of the non-conductive filler relative to the total mass of the second agent is 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by 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 10% by 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 10% by mass or more.

[0121] <Additives> In the curable composition preparation kit of the present disclosure, at least one of the first and second parts may independently 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, such as camphorquinone (CQ) and ethyl dimethylaminobenzoate (EDB). Furthermore, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecylammonium chloride, and triclosan may also be incorporated. Known dyes and pigments may also be incorporated into the curable composition preparation kit of the present disclosure.

[0122] The hardenable composition preparation kit of the present disclosure is preferably used to prepare a hardenable composition for dental materials. Hardenable compositions for dental materials are not particularly limited, and examples thereof include dental adhesives, dental filling materials, dental sealants (dental fissure sealants), core builders, 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 or the hardenable composition of the present disclosure described below is particularly preferably used as a dental adhesive. Examples of dental adhesives include dental adhesive resin cements, orthodontic adhesives, adhesives for fixing loose teeth, cavity adhesives, 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.

[0123] <Curable Composition> The curable composition of the present disclosure contains the ascorbic acid derivative of the present disclosure, a transition metal compound, an organic peroxide, and a monomer. When the curable composition of the present disclosure contains the above-described components, polymerizability can be favorably improved. Specific examples, preferred aspects, etc. of the monomer in the curable composition are the same as those of the monomer described above. It is preferable that the curable composition of the present disclosure further contains 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. The curable composition of the present disclosure may contain the additives described above.

[0124] <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 includes the cured product of the present disclosure.

[0125] Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples. Hereinafter, the compound represented by formula (1) will also be referred to as "formula (1) compound".

[0126] The components used in this example are shown below.

[0127] <Polymerization inhibitor> BHT: 2,6-di-tert-butyl-p-cresol

[0128] <Monomers not containing an acidic group> 2-HPMA: 2-hydroxypropyl methacrylate TEGDMA: triethylene glycol dimethacrylate UDMA: trimethylhexyl diurethane hydroxymethacrylate

[0129] <Acidic group-containing monomer> MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[0130] <Filler> R812: AEROSIL® R812 manufactured by Evonik SG-YBF100WS CMP10: Ytterbium filler, 0.1 μm IS TGF2722A: IS TGF 2722 A manufactured by Ferro 1.0 μm, silane coupling agent treatment amount 9%

[0131] <Transition metal compound> Cu(OAc)2 monohydrate: copper acetate monohydrate

[0132] <Organic peroxide> Luperox TAH: tert-amyl hydroperoxide

[0133] <Polymerization accelerator> DBPPP: tetrakis(2,4-di-tert-butylphenyl)[1,1'-biphenyl]-4,4'-diylbis(phosphonite) ATH: acetylthiourea

[0134] <Photopolymerization initiator> CQ: camphorquinone BEDB: 2-butoxyethyl-4-(dimethylamino)benzoate

[0135] <Specific Ascorbic Acid Derivative (more specifically, TiPrSiOAA as a specific ascorbic acid compound (i.e., an ascorbic acid compound containing a structure in which the hydrogen atom in at least one of the hydroxyl groups contained in ascorbic acid is replaced with a silicon atom), or CaTiPrSiOAA as a salt of the specific ascorbic acid compound)>

[0136]

[0137] <Other ascorbic acids (AA, AS6P)>

[0138]

[0139] <Other silyl compounds> MPTS: 3-methacryloyloxypropyltrimethoxysilane

[0140] [Synthesis Examples of Ascorbic Acid Derivatives] Synthesis examples of the specific examples of the ascorbic acid derivatives described above are shown below.

[0141] Synthesis Example 1 (Synthesis of TiPrSiOAA as specific ascorbic acid compound) According to the following scheme, TiPrSiOAA was synthesized as a specific ascorbic acid compound (i.e., an ascorbic acid compound containing a structure in which the hydrogen atom in at least one of the hydroxyl groups contained in ascorbic acid is replaced with a silicon atom).

[0142]

[0143] The detailed procedure of the above scheme is as follows: Under nitrogen, ascorbic acid (AA) (2.290 g, 13 mmol) and potassium carbonate (K ２ CO ３ ) (5.390 g, 39 mmol) was dissolved in N,N-dimethylformamide (DMF) (4.579 mL), and a solution of benzyl bromide (BnBr) (4.447 g, 26 mmol) dissolved in 4.579 mL of N,N-dimethylformamide was added dropwise thereto, followed by stirring at 50°C. After 3.5 hours, the mixture was filtered through Celite, and the residue was washed with ethyl acetate (9.159 mL). Water (27.474 mL) and ethyl acetate (18.316 mL) were added to the obtained filtrate, and the layers were separated and extracted three times with ethyl acetate. The obtained organic layers were combined and washed with water (82.422 mL). The obtained organic layer was washed with saturated brine (82.422 mL). The obtained organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain a brown oil. The resulting brown oil was purified by silica gel column chromatography to obtain the target 2,3-O-dibenzyl ascorbic acid (2,3-O-diBnAA) (2.316 g, 6.5 mmmol, yield 50%) as a pale yellow transparent oil.

[0144] Under nitrogen, 2,3-O-dibenzyl ascorbic acid (2,3-O-diBnAA) (2.316 g, 6.5 mmol) and imidazole (885 mg, 13 mmol) were stirred and dissolved in tetrahydrofuran (THF) (69.492 mL). 1,3-Dichloro-1,1,3,3-tetraisopropyldisiloxane (2.050 g, 7 mmol) was added dropwise to the solution, and the mixture was stirred at room temperature for 5 hours. After stirring, the mixture was concentrated under reduced pressure, and the resulting residue was extracted three times with water (104.238 mL) and ethyl acetate (104.238 mL). The resulting organic layers were combined and washed with water (312.714 mL). The resulting organic layer was washed with 312.714 mL of saturated brine. The resulting organic layer was dried over sodium sulfate and concentrated under reduced pressure to give 5,6-O-tetraisopropyldisiloxy-2,3-O-dibenzyl ascorbic acid (TiPrSiO-2,3-O-diBnAA) (3.503 g, 5.9 mol, crude yield 90%) as a yellow transparent oil.

[0145] In the presence of nitrogen, 5,6-O-tetraisopropyldisiloxy-2,3-O-dibenzyl ascorbic acid (TiPrSiO-2,3-O-diBnAA) (3.503 g, 5.9 mol) and 10% Pd / C (88 mg) were added to tetrahydrofuran (THF) (88.335 mL). The atmosphere was then replaced with hydrogen and stirred for 10 hours. The reaction solution was filtered through Celite, and the residue was washed with 8.834 mL of tetrahydrofuran. The resulting organic layer was concentrated under reduced pressure. The resulting yellow oily residue was purified by silica gel column chromatography to obtain the desired pale yellow-white crystalline 5,6-O-tetraisopropyldisiloxyascorbic acid (TiPrSiOAA) (1.235 g, 3.0 mmol, 50% yield).

[0146] TiPrSiOAA １ H-NMR (CD ３ The assignments by OD are shown below. １ H-NMR: δ4.69 (d, J = 1.0Hz, 1H), 4.31 (dt, J = 8.0 and 1.7Hz, 1H), 4.04-3.96 (m, 2H), 1.10-0.88 (m, 32H), ppm

[0147] Synthesis Example 2 (Synthesis of CaTiPrSiOAA as a salt of a specific ascorbic acid compound) CaTiPrSiOAA as a salt of a specific ascorbic acid compound was synthesized according to the following scheme.

[0148]

[0149] The detailed procedure of the above scheme is as follows: 5,6-O-tetraisopropyldisiloxyascorbic acid (TiPrSiOAA) (836 mg, 2.0 mmol) was charged into 1005 mL of tetrahydrofuran (THF). After cooling to 0°C, 20 mM calcium hydroxide (Ca(OH) ２ A 1.0 mmol aqueous solution of 5,6-O-tetraisopropyldisiloxyascorbate (CaTiPrSiOAA) was added dropwise, and the mixture was stirred at 0°C for 16 hours. The progress of the reaction was confirmed by IR measurement (measured at room temperature by ATR using a PerkinElmer Spectrum 2). The mixture was then concentrated under reduced pressure and freeze-dried to obtain calcium 5,6-O-tetraisopropyldisiloxyascorbate (CaTiPrSiOAA) (756 mg, yield 87%).

[0150] Examples 1 to 2 and Comparative Examples 1 to 3 Preparation of a kit for preparing a curable composition (first agent and second agent) As the first agent and the second agent for the kit for preparing a curable composition, a first agent and a second agent were prepared, respectively, having the compositions shown in Table 1. The numbers in the column for each component shown in Table 1 indicate the amount (parts by mass) of each component.

[0151] <Evaluation of Adhesion> A bovine mandibular anterior tooth was subjected to root amputation and pulp removal, and then placed in a plastic cylindrical container with a diameter of 25 mm and a depth of 25 mm and embedded in acrylic resin. This was used as a bovine tooth adherend. The bovine tooth adherend was polished with waterproof emery paper (P400) immediately before use to remove the smooth surface of the bovine tooth dentin (hereinafter referred to as the "adhesion surface of the bovine tooth adherend").

[0152] The adhesive properties of the curable compositions were evaluated in accordance with ISO 16506 using the first and second parts of each Example and Comparative Example, the bovine tooth adherends, and the cylindrical cured product described below.

[0153] Specifically, excess moisture on the adherend surface of the bovine tooth adherend was wiped off with a Kimwipe, and a drop of water was dropped onto the adherend. Next, the first and second parts listed in Table 1 were mixed for 20 seconds to form a curable composition, and an appropriate amount of this curable composition was applied to the adherend surface of a cylindrical cured product of the filler composition (Vinus Diamond, manufactured by Kulzer, the adherend surface of which had been previously polished with waterproof emery paper P180). Next, the adherend surface of the bovine tooth adherend and the adherend surface of the cylindrical cured product coated with the curable composition were bonded, and the cylindrical cured product was placed on the bovine tooth adherend. Then, using a dedicated jig, the cylindrical cured product and the bovine tooth adherend were pressed together with a force of 5 N. Next, excess curable composition was removed from the bonded joint between the bovine tooth adherend and the cylindrical cured product, and the bonded bovine tooth adherend and cylindrical cured product were then left to stand at 37°C for 40 minutes while attached to a dedicated jig, then at 37°C for 60 minutes while removed from the jig, and then left to stand in a thermostatic bath at 37°C for 24 hours. The adhesive strength between the bovine tooth adherend and the cylindrical cured product was then measured. The adhesive strength was determined by applying a shear load parallel to the bovine tooth adherend and in contact with the surface (i.e., the adherend surface of the bovine tooth adherend) at a crosshead speed of 1.0 mm / min, and measuring the shear load at which the cylindrical cured product adhered to the bovine tooth adherend peeled from the surface.

[0154] Based on the obtained adhesive strength, the adhesiveness was evaluated according to the following criteria. The results are shown in Table 1. In the following criteria, the most excellent rank in adhesiveness is "A". (Criteria) A: Adhesive strength is 15.0 MPa or more. B: Adhesive strength is 14.5 MPa or more and less than 15.0 MPa. C: Adhesive strength is 14.0 MPa or more and less than 14.5 MPa. D: Adhesive strength is 13.5 MPa or more and less than 14.0 MPa. E: Adhesive strength is less than 13.5 MPa.

[0155]

[0156] As shown in Table 1, each of the Examples using the ascorbic acid derivative, which is the compound of formula (1) or a salt thereof, exhibited excellent adhesiveness of the curable composition compared to Comparative Examples 1 and 2, which used comparative ascorbic acid, and other silyl compounds (i.e., silyl compounds that are neither the compound of formula (1) nor a salt thereof).

[0157] The disclosure of Japanese Patent Application No. 2024-024350, filed on February 21, 2024, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. An ascorbic acid derivative, which is an ascorbic acid compound or a salt thereof containing a structure in which the hydrogen atom of at least one of the hydroxyl groups contained in ascorbic acid is replaced with a silicon atom.

2. The ascorbic acid derivative according to claim 1, wherein the ascorbic acid compound comprises a structure represented by the following formula (A): [In formula (A), A １１ and A １２ is a group represented by formula (A1), and A １１ and A １２ The other is a hydrogen atom or a group represented by formula (A1). In formula (A1), all four *s indicate bonding positions.

3. The ascorbic acid derivative according to claim 1, wherein the ascorbic acid compound is a compound represented by the following formula (B1) or (B2): [In formula (B1), X １ and X ２ is a group represented by formula (X), and X １ and X ２ The other is a hydrogen atom or a group represented by formula (X). When two groups represented by formula (X) are present in formula (B1), the two groups represented by formula (X) may be the same or different. １ ~R ３ are each independently a monovalent organic group, and * represents a bonding position. ４ ~R ７ are each independently a monovalent organic group.

4. A polymerization initiator additive comprising the ascorbic acid derivative according to any one of claims 1 to 3.

5. A polymerization initiator comprising the ascorbic acid derivative according to any one of claims 1 to 3, a transition metal compound, and an organic peroxide.

6. A kit for preparing a curable composition, comprising: a first agent containing a monomer (A); and a second agent containing a monomer (B), wherein the combined components of the first agent and the second agent contain the ascorbic acid derivative, transition metal compound, and organic peroxide described in any one of claims 1 to 3.

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

8. The kit for preparing a curable composition according to claim 6, wherein at least one of the monomer (A) in the first part and the monomer (B) in the second part contains an acidic group-containing monomer.

9. The kit for preparing a curable composition according to claim 6, wherein the monomer (A) in the first part contains an acidic group-containing monomer, and the second part contains the ascorbic acid derivative.

10. The kit for preparing a curable composition according to claim 6, wherein at least one of the first agent and the second agent contains a polymerization accelerator (1) that is at least one selected from the group consisting of phosphonite compounds, phosphite compounds, and sulfite compounds.

11. The kit for preparing a curable composition according to claim 10, wherein the second agent comprises the ascorbic acid derivative and the polymerization accelerator (1).

12. The kit for preparing a curable composition according to claim 6, wherein at least one of the first part and the second part contains a filler.

13. The kit for preparing a curable composition according to claim 6, wherein the total content of the ascorbic acid derivative in the first agent and the second agent is 0.1% by mass to 5% by mass, based on the total mass of the curable composition to be prepared.

14. The kit for preparing a hardenable composition according to claim 6, which is used to prepare a hardenable composition for dental materials.

15. A curable composition comprising the ascorbic acid derivative according to any one of claims 1 to 3, a transition metal compound, an organic peroxide, and a monomer.

16. A cured product of the curable composition according to claim 15.

17. A dental material comprising the hardened product according to claim 16.

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