Thiourethane (METH)acrylate compound, monomer composition, curable composition, and dental material

Abstract

Provided is a thiourethane (meth)acrylate compound having two bonds represented by formula (X), two urethane bonds, and two (meth)acryloyl groups. In formula (X), the two * symbols are each a bonding site.

Description

Thiourethane (meth)acrylate compound, monomer composition, hardenable composition, and dental material

[0001] The present disclosure relates to thiourethane (meth)acrylate compounds, monomer compositions, hardenable compositions, and dental materials.

[0002] Dental material compositions such as composite resins generally contain a dental material composition containing a monomer, a polymerization initiator, etc. As the dental material composition, a composition containing a polyfunctional methacrylate, which is a radically polymerizable monomer, is sometimes used from the viewpoints of the safety of the contained monomer in vivo, the mechanical strength of the cured product, the abrasion resistance of the cured product, etc. As a composition containing a polyfunctional methacrylate, a composition containing the polyfunctional methacrylate UDMA (urethane dimethacrylate with CAS number 72869-86-4) is known (see, for example, Patent Document 1).

[0003] Patent Document 1: Japanese Patent Publication No. 2002-518419

[0004] For example, in the dental field, excellent bending strength is sometimes required for a cured product obtained by curing a composition containing a monomer.

[0005] However, the above-mentioned UDMA, which has been conventionally used in the dental field, has room for improvement in terms of the bending strength of the cured product, and therefore, there has been a demand for a (meth)acrylate that can impart excellent bending strength to the cured product.

[0006] An object of one embodiment of the present disclosure is to provide a thiourethane (meth)acrylate compound, a monomer composition, a curable composition, and a dental material that can impart excellent flexural strength to a cured product.

[0007] Specific means for solving the above problems are as follows: <1> A thiourethane (meth)acrylate compound including two bonds represented by the following formula (X), two urethane bonds, and two (meth)acryloyl groups:

[0008]

[0009] In formula (X), the two * symbols each represent a bonding position.

[0010] <2> The thiourethane (meth)acrylate compound according to <1>, which is a reaction product of a thiol compound (B) containing two mercapto groups, a (meth)acrylate compound (C) containing one hydroxy group and one (meth)acryloyloxy group, and an isocyanate compound (D) containing two isocyanate groups. <3> The thiourethane (meth)acrylate compound according to <1> or <2>, which is a compound represented by the following formula (A1):

[0011]

[0012] In formula (A1), R １Ａ is a residue obtained by removing two mercapto groups from a thiol compound (B) containing two mercapto groups, and R ２Ａ is a residue obtained by removing two isocyanate groups from an isocyanate compound (D) containing two isocyanate groups, and R ３Ａ is a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from a (meth)acrylate compound (C) containing one hydroxy group and one (meth)acryloyloxy group, and R ４Ａ is a hydrogen atom or a methyl group, and two R ２Ａ may be the same or different, and two R ３Ａ may be the same or different, and two R ４Ａ may be the same or different.

[0013] <4> The thiourethane (meth)acrylate compound according to <2> or <3>, wherein the isocyanate compound (D) includes a compound represented by any one of the following formulas (D1) to (D8):

[0014]

[0015] <5> The thiourethane (meth)acrylate compound according to any one of <2> to <4>, wherein the thiol compound (B) includes a compound represented by the following formula (B1):

[0016]

[0017] In formula (B1), R Ｂ is a divalent organic group having 1 to 20 carbon atoms.

[0018] <6> The thiourethane (meth)acrylate compound according to any one of <2> to <5>, wherein the (meth)acrylate compound (C) includes a compound represented by the following formula (C1):

[0019]

[0020] In formula (C1), R １Ｃ is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R ２Ｃ is a hydrogen atom or a methyl group.

[0021] <7> A monomer composition comprising the thiourethane (meth)acrylate compound according to any one of <1> to <6>. <8> The monomer composition according to <7>, which is used for a dental material. <9> A curable composition comprising the thiourethane (meth)acrylate compound according to any one of <1> to <6> and a polymerization initiator. <10> A dental material comprising the curable composition according to <9> or a cured product of the curable composition.

[0022] According to one aspect of the present disclosure, there are provided a thiourethane (meth)acrylate compound, a monomer composition, a hardenable composition, and a dental material that can impart excellent flexural strength to a cured product.

[0023]

[0033] FIG. 1 is an infrared absorption spectrum of Monomer 1, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0034] FIG. 2 is an infrared absorption spectrum of Monomer 2, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0035] FIG. 3 is an infrared absorption spectrum of Monomer 3, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0036] FIG. 4 is an infrared absorption spectrum of Monomer 4, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0037] FIG. 5 is an infrared absorption spectrum of Monomer 5, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0038] FIG. 6 is an infrared absorption spectrum of Monomer 6, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0039] FIG. 7 is an infrared absorption spectrum of Monomer 7, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0039] FIG. 8 is an infrared absorption spectrum of Monomer 8, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0039] FIG. 9 is an infrared absorption spectrum of Monomer 9, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0039] FIG. 10 is an infrared absorption spectrum of Monomer 11, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0033] FIG. 1 is an infrared absorption spectrum of Monomer 12, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0034] FIG. 2 is an infrared absorption spectrum of Monomer 13, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0035] FIG. 3 is an infrared absorption spectrum of Monomer 14, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0036] FIG. 4 is an infrared absorption spectrum of Monomer 15, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0037] FIG. 5 is an infrared absorption spectrum of Monomer 16, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0038] FIG. 6 is an infrared absorption spectrum of Monomer 17, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0039] FIG. 7 is an infrared absorption spectrum of Monomer 18, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0039] FIG. 8 is an infrared absorption spectrum of Monomer 19, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.1 shows an infrared absorption spectrum of Monomer 20, a specific example of a thiourethane (meth)acrylate compound of the present disclosure; 21, a specific example of a thiourethane (meth)acrylate compound of the present disclosure; and 22, a specific example of a thiourethane (meth)acrylate compound of the present disclosure.

[0024] In this 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 this disclosure, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In this disclosure, when there are multiple substances corresponding to each component, the amount of each component means the total amount of multiple substances unless otherwise specified. In this disclosure, "(meth)acryloyl group" means an acryloyl group and a methacryloyl group, and "(meth)acrylate" means an acrylate and a methacrylate.

[0025] [Thiourethane (meth)acrylate compound (A)] The thiourethane (meth)acrylate compound of the present disclosure (also referred to as "thiourethane (meth)acrylate compound (A)" in the present disclosure) contains two bonds represented by the following formula (X) (i.e., thiourethane bonds), two urethane bonds, and two (meth)acryloyl groups:

[0026]

[0027] In formula (X), the two * symbols each represent a bonding position.

[0028] The thiourethane (meth)acrylate compound (A) (i.e., the thiourethane (meth)acrylate compound of the present disclosure) can impart excellent flexural strength to a cured product. Here, the term "cured product" refers to a cured product obtained by curing the thiourethane (meth)acrylate compound (A) alone or a composition containing the thiourethane (meth)acrylate compound (A). That is, the cured product has excellent flexural strength (e.g., breaking strength and elastic modulus in a bending test). This effect is thought to be obtained by the combination of the two bonds represented by formula (X) (i.e., thiourethane bonds), two urethane bonds, and two (meth)acryloyl groups contained in the thiourethane (meth)acrylate compound (A).

[0029] The molecular weight of the thiourethane (meth)acrylate compound (A) is not particularly limited as long as it contains two bonds represented by formula (X), two urethane bonds, and two (meth)acryloyl groups. The molecular weight of the thiourethane (meth)acrylate compound (A) is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,500 or less, and even more preferably 1,300 or less. The lower limit of the molecular weight of the thiourethane (meth)acrylate compound (A) is not particularly limited as long as it contains two bonds represented by formula (X), two urethane bonds, and two (meth)acryloyl groups.

[0030] The thiourethane (meth)acrylate compound (A) is preferably a reaction product of a thiol compound (B) containing two mercapto groups, a (meth)acrylate compound (C) containing one hydroxy group and one (meth)acryloyloxy group, and an isocyanate compound (D) containing two isocyanate groups. In this case, a thiourethane bond is formed by the reaction between the mercapto group (also known as a thiol group) in the thiol compound (B) and the isocyanate group in the isocyanate compound (D), and a urethane bond is formed by the reaction between the hydroxy group in the (meth)acrylate compound (C) and the isocyanate group in the isocyanate compound (D).

[0031] When the thiourethane (meth)acrylate compound (A) is the above-mentioned reaction product, each of the thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D) may be one type or two or more types.

[0032] In Tables 1 and 2 in the Examples section described later, the thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D) are referred to as thiol (B), (meth)acrylate (C), and isocyanate (D), respectively.

[0033] <Compound Represented by Formula (A1)> The thiourethane (meth)acrylate compound (A) (for example, a reaction product of a thiol compound (B), a (meth)acrylate compound (C), and an isocyanate compound (D)) is preferably a compound represented by the following formula (A1):

[0034]

[0035] In formula (A1), R １Ａ is a residue obtained by removing two mercapto groups from a thiol compound (B) containing two mercapto groups, and R ２Ａ is a residue obtained by removing two isocyanate groups from an isocyanate compound (D) containing two isocyanate groups, and R ３Ａ is a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from a (meth)acrylate compound (C) containing one hydroxy group and one (meth)acryloyloxy group, and R ４Ａ is a hydrogen atom or a methyl group, and two R ２Ａ may be the same or different, and two R ３Ａ may be the same or different, and two R ４Ａ may be the same or different.

[0036] Preferred embodiments of raw materials (i.e., thiol compound (B), (meth)acrylate compound (C), and isocyanate compound (D)) for producing the thiourethane (meth)acrylate compound (A) (for example, the above-mentioned reaction product and the compound represented by formula (A1)) are shown below.

[0037] <Thiol Compound (B)> The thiol compound (B) is a compound containing two mercapto groups.

[0038] The molecular weight of the thiol compound (B) is preferably 1,000 or less, more preferably 500 or less, and even more preferably 400 or less.

[0039] The thiol compound (B) preferably contains a compound represented by the following formula (B1):

[0040] In formula (B1), R Ｂ is a divalent organic group having 1 to 20 carbon atoms.

[0041] R Ｂ The divalent organic group represented by R may contain a hydrocarbon group. Ｂ The divalent organic group represented by the formula (I) may further contain an ester bond, an ether bond, a sulfide bond, or the like.

[0042] The proportion of the compound represented by formula (B1) in the thiol compound (B) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.

[0043] The compound represented by formula (B1) preferably contains a thiol compound represented by any one of the following formulae (B-1) to (B-5):

[0044]

[0045] In formula (B1-1), R is a divalent hydrocarbon group having 1 to 20 carbon atoms. The divalent hydrocarbon group represented by R is preferably an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), an arylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (e.g., a phenylene group), an alkylenearylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (e.g., a methylenephenylene group), or an alkylenearylenealkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (e.g., a methylenephenylenemethylene group). In formula (B1-4), n is an integer of 1 to 10.

[0046] The total proportion of the thiol compounds represented by any one of Formulas (B-1) to (B-5) in the thiol compound (B) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.

[0047] <(Meth)acrylate Compound (C)> The (meth)acrylate compound (C) is a compound containing one hydroxy group and one (meth)acryloyloxy group.

[0048] The molecular weight of the (meth)acrylate compound (C) is preferably 1,000 or less, more preferably 500 or less, and even more preferably 400 or less.

[0049] The (meth)acrylate compound (C) preferably includes a compound represented by the following formula (C1):

[0050]

[0051] In formula (C1), R １Ｃ is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R ２Ｃ is a hydrogen atom or a methyl group.

[0052] R １Ｃ The divalent organic group represented by R may contain a hydroxy group and a hydrocarbon group. Ｂ The divalent organic group represented by the formula (I) may further contain an ester bond, an ether bond, a sulfide bond, or the like.

[0053] The proportion of the compound represented by formula (C1) in the (meth)acrylate compound (C) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.

[0054] Examples of the (meth)acrylate compound (C) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate.

[0055] The (meth)acrylate compound (C) preferably contains at least one selected from the group consisting of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxybutyl acrylate (2HBA), 2-hydroxybutyl methacrylate (2HBMA), 4-hydroxybutyl acrylate (4HBA), 4-hydroxybutyl methacrylate (4HBMA), 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexanedimethanol monomethacrylate.

[0056] <Isocyanate Compound (D)> The isocyanate compound (D) is a compound containing two isocyanate groups.

[0057] The molecular weight of the isocyanate compound (D) is preferably 1,000 or less, more preferably 500 or less, and even more preferably 400 or less.

[0058] The isocyanate compound (D) preferably contains a compound represented by any one of the following formulas (D1) to (D8):

[0059]

[0060] The total proportion of the compounds represented by any one of Formulas (D1) to (D8) in the isocyanate compound (D) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.

[0061] <Example of a method for producing a thiourethane (meth)acrylate compound (Production method X)> Hereinafter, an example of a production method for producing a thiourethane (meth)acrylate compound (A) (hereinafter also referred to as "Production method X") will be described.

[0062] Production method X includes a reaction step of reacting the above-mentioned thiol compound (B), the above-mentioned (meth)acrylate compound (C), and the above-mentioned isocyanate compound (D) to produce a thiourethane (meth)acrylate compound (A). Production method X may include other steps as necessary. According to production method X, a thiourethane (meth)acrylate compound (A) (e.g., a compound represented by formula (A1)) is produced as a reaction product of the above-mentioned thiol compound (B), the above-mentioned (meth)acrylate compound (C), and the above-mentioned isocyanate compound (D).

[0063] In Production Method X, the molar ratio of mercapto groups contained in the total amount of charged thiol compound (B) to isocyanate groups contained in the total amount of charged isocyanate compound (D) (hereinafter also referred to as the "charge molar ratio [SH / NCO]" or simply "SH / NCO") is preferably 0.01 to 0.50, more preferably 0.02 to 0.40, and preferably 0.03 to 0.30.

[0064] In Production Method X, the molar ratio of hydroxy groups contained in the total amount of (meth)acrylate compound (C) charged to the total amount of isocyanate compound (D) charged (hereinafter also referred to as the "charge molar ratio [OH / NCO]" or simply "OH / NCO") is set to the molar ratio of OH in the (meth)acrylate compound (C) to NCO, taking into consideration the molar ratio of SH in the thiol compound (B), so that as little unreacted NCO as possible remains in the isocyanate compound (D) in the final thiourethane (meth)acrylate compound (A) after synthesis. For example, it is preferably 0.50 to 1.50, more preferably 0.60 to 0.99, and even more preferably 0.70 to 0.97.

[0065] In Production Method X, the molar ratio of the sum of the mercapto groups contained in the total amount of the thiol compound (B) and the hydroxy groups contained in the total amount of the (meth)acrylate compound (C) to the isocyanate groups contained in the total amount of the isocyanate compound (D) (hereinafter also referred to as the "charge molar ratio [(SH+OH) / NCO]" or simply "(SH+OH) / NCO") is preferably 1.00 to 2.00, more preferably 1.00 to 1.50, and even more preferably 1.00 to 1.30.

[0066] The reaction in Production Method X may be carried out in a solvent or without a solvent. Any known solvent can be used as long as it is inert to the reaction. Examples of the solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and perclene; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used alone or in combination.

[0067] (Catalyst) A catalyst may be used in the above reaction in Production Method X. Examples of the catalyst include: organotin compounds such as dibutyltin dilaurate, dibutyltin dioctate, and tin octoate; organometallic compounds other than tin compounds such as copper naphthenate, cobalt naphthenate, zinc naphthenate, zirconium acetylacetonate, iron acetylacetonate, and germanium acetylacetonate; amine compounds such as triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undecene, N,N-dimethylcyclohexylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-pentamethyldiethylenetriamine, N,N,N',N'-tetra(3-dimethylaminopropyl)-methanediamine, N,N'-dimethylpiperazine, and 1,2-dimethylimidazole, and salts thereof; trialkylphosphine compounds such as tri-n-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine, and tri-n-octylphosphine; and the like. Of these, dibutyltin dilaurate and tin octoate are preferred.

[0068] The amount of the catalyst used may be 0.001% by mass to 1.0% by mass, or may be 0.01% by mass to 0.5% by mass, based on the total amount of the thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D).

[0069] The reaction temperature is not particularly limited and is, for example, 20°C to 120°C, preferably 30°C to 100°C, and more preferably 50°C to 100°C.

[0070] The reaction time is not particularly limited as it depends on conditions such as the reaction temperature, and is, for example, 5 minutes to 50 hours. The end point of the reaction can be confirmed by analysis by HPLC (high performance liquid chromatography), etc.

[0071] A polymerization inhibitor may be used during the above reaction in Production Method X. Examples of the polymerization inhibitor include dibutylhydroxytoluene (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), and phenothiazine (PTZ).

[0072] The amount of the polymerization inhibitor used may be 0.001% by mass to 0.5% by mass, 0.002% by mass to 0.3% by mass, or 0.005% by mass to 0.3% by mass, relative to the total amount of the thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D).

[0073] [Monomer Composition] The monomer composition of the present disclosure contains at least one thiourethane (meth)acrylate compound (A) (i.e., the thiourethane (meth)acrylate compound of the present disclosure).

[0074] The monomer composition of the present disclosure contains at least one thiourethane(meth)acrylate compound (A), and therefore exhibits an effect similar to that of the thiourethane(meth)acrylate compound (A) (i.e., the effect of imparting excellent bending strength (e.g., breaking strength and elastic modulus in a bending test) to a cured product).

[0075] The content of the thiourethane (meth)acrylate compound (A) relative to the total amount of the monomer composition of the present disclosure may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, 80% by mass or more, or 90% by mass or more. The upper limit of the content of the thiourethane (meth)acrylate compound (A) relative to the total amount of the monomer composition of the present disclosure may be, for example, 99% by mass, 95% by mass, 90% by mass, etc. For example, the monomer composition of the present disclosure may be a composition consisting of a thiourethane (meth)acrylate compound (A) content of 90% by mass or more and impurities.

[0076] Furthermore, the monomer composition of the present disclosure may contain a (meth)acrylate compound other than the thiourethane (meth)acrylate compound (A) (hereinafter also referred to as "(meth)acrylate compound (E)").

[0077] Examples of the (meth)acrylate compound (E) include neopentyl di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, poly(meth)acrylate, methyl ... Examples of the (meth)acrylate compound (E) include polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (urethane dimethacrylate: UDMA), etc. The (meth)acrylate compound (E) may be used alone or in combination of two or more.

[0078] For example, a viscosity-adjusting monomer such as triethylene glycol dimethacrylate may be used to adjust the viscosity of the monomer composition to a low level. When the viscosity-adjusting monomer and the thiourethane (meth)acrylate (A) are used in combination, the viscosity-adjusting monomer and the thiourethane (meth)acrylate (A) may be used in a mass ratio of 1:0.8 to 1.2, or 1:0.8 to 4.0 (preferably 1:1.1 to 4.0).

[0079] When the monomer composition of the present disclosure contains a (meth)acrylate compound (E), the proportion of the (meth)acrylate compound (E) in the monomer composition is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and even more preferably 20% by mass to 60% by mass. When the monomer composition of the present disclosure contains a (meth)acrylate compound (E), the proportion of the thiourethane (meth)acrylate (A) in the monomer composition is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and even more preferably 40% by mass to 80% by mass.

[0080] The use of the monomer composition of the present disclosure is not particularly limited. The monomer composition of the present disclosure is preferably a monomer composition for dental materials. Specific examples of dental materials will be described later.

[0081] <Curable Composition> The curable composition of the present disclosure contains a thiourethane (meth)acrylate compound (A) (i.e., the thiourethane (meth)acrylate compound of the present disclosure) and a polymerization initiator. The curable composition of the present disclosure may also contain other components (for example, a (meth)acrylate compound (E)).

[0082] The curable composition of the present disclosure contains at least one thiourethane(meth)acrylate compound (A), and therefore exhibits an effect similar to that of the thiourethane(meth)acrylate compound (A) (i.e., the effect of imparting excellent bending strength (e.g., breaking strength and elastic modulus in a bending test) to a cured product).

[0083] The use of the hardenable composition of the present disclosure is not particularly limited. The hardenable composition of the present disclosure is preferably a hardenable composition for dental materials. Specific examples of dental materials will be described later.

[0084] The proportion of the thiourethane (meth)acrylate compound (A) in the curable composition of the present disclosure is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, even more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass.

[0085] The curable composition of the present disclosure includes at least one polymerization initiator. As the polymerization initiator, for example, a general polymerization initiator used in the dental field can be used.

[0086] When polymerization is carried out at room temperature, the polymerization initiator is preferably, for example, a redox polymerization initiator that combines an oxidizing agent and a reducing agent. When a redox polymerization initiator is used, the oxidizing agent and the reducing agent are packaged separately, and the two are mixed immediately before use.

[0087] The oxidizing agent is not particularly limited, and examples thereof include diacyl peroxides (e.g., benzoyl peroxide), peroxy esters (e.g., t-butyl peroxybenzoate), dialkyl peroxides (e.g., dicumyl peroxide), peroxy ketals (e.g., 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane), ketone peroxides (e.g., methyl ethyl ketone peroxide), and organic peroxides such as hydroperoxides (e.g., t-butyl hydroperoxide).

[0088] The reducing agent is not particularly limited, and a tertiary amine (N,N-dimethylaniline, etc.) is usually used.

[0089] In addition to these organic peroxide / amine systems, there are also cumene hydroperoxide / thiourea systems, ascorbic acid / Cu systems, ２＋ Redox polymerization initiators such as salt-based initiators, organic peroxide / amine / sulfinic acid (or its salt)-based initiators, etc. Tributylborane, organic sulfinic acid, etc. are also preferably used as the polymerization initiator.

[0090] When thermal polymerization is performed by heating, polymerization initiators such as peroxides and azo compounds are preferred. The peroxides are not particularly limited, and examples thereof include benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. The azo compounds are not particularly limited, and examples thereof include azobisisobutyronitrile.

[0091] When photopolymerization is performed by irradiation with visible light, redox initiators such as α-diketone / tertiary amine, α-diketone / aldehyde, and α-diketone / mercaptan are preferred. The photopolymerization initiator is not particularly limited, and examples include α-diketone / reducing agent, ketal / reducing agent, and thioxanthone / reducing agent. Examples of α-diketones include camphorquinone. Examples of ketals include benzyl dimethyl ketal. Examples of thioxanthones include 2-chlorothioxanthone. Examples of reducing agents include tertiary amines (e.g., Michler's ketone), aldehydes (e.g., citronellal), and compounds having a thiol group (e.g., 2-mercaptobenzoxazole). Systems such as α-diketone / organic peroxide / reducing agent, in which an organic peroxide is added to these redox systems, are also suitable.

[0092] When photopolymerization is carried out by irradiation with ultraviolet light, photopolymerization initiators such as benzoin alkyl ether, benzil dimethyl ketal, etc. are preferred. Photopolymerization initiators such as (bis)acylphosphine oxides are also preferably used.

[0093] Examples of (bis)acylphosphine oxides include acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.) and bisacylphosphine oxides (bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, etc.). These (bis)acylphosphine oxide photopolymerization initiators may be used alone or in combination with reducing agents such as various amines, aldehydes, mercaptans, and sulfinates. These (bis)acylphosphine oxide photopolymerization initiators may also be used in combination with the above-mentioned visible light photopolymerization initiators.

[0094] The polymerization initiator may be used by referring to, for example, WO 2021 / 29406, WO 2019 / 107323, WO 2020 / 040141, etc.

[0095] The proportion of the polymerization initiator in the curable composition of the present disclosure is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 5% by mass.

[0096] The curable composition of the present disclosure may contain at least one filler. A typical filler used in the dental field can be used as the filler. Fillers are generally broadly classified into organic fillers and inorganic fillers. Examples of organic fillers include fine powders of polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, and the like.

[0097] Examples of inorganic fillers include fine powders of various glasses (mainly composed of silicon dioxide and optionally containing oxides of heavy metals, boron, aluminum, etc.), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite, etc. Specific examples of such inorganic fillers include barium borosilicate glass, strontium boroaluminosilicate glass, lanthanum glass, fluoroaluminosilicate glass, boroaluminosilicate glass, etc.

[0098] The filler may be used by referring to, for example, International Publication No. 2021 / 29406, International Publication No. 2019 / 107323, International Publication No. 2020 / 040141, etc.

[0099] The amount of the filler to be blended is preferably 10 parts by mass to 2,000 parts by mass, more preferably 50 parts by mass to 1,000 parts by mass, and even more preferably 100 parts by mass to 600 parts by mass, relative to 100 parts by mass of all components other than the filler contained in the curable composition.

[0100] The curable composition of the present disclosure may contain other components in addition to those described above, such as a polymerization inhibitor, a colorant (e.g., a pigment, a dye, etc.), a reinforcing material (e.g., a fiber, etc.), a bactericide, a disinfectant, a stabilizer, a preservative, etc.

[0101] The curable composition of the present disclosure can be cured under appropriate conditions using the polymerization method of the polymerization initiator described above. For example, in the case of a curable composition of the present disclosure containing a photopolymerization initiator for visible light irradiation, the curable composition can be processed into a predetermined shape and then irradiated with visible light for a predetermined period of time using a known light irradiation device to obtain a desired cured product. Conditions such as irradiation intensity can be appropriately changed depending on the curability of the curable composition. In addition, the cured product cured by light irradiation, including visible light, may be further heat-treated under appropriate conditions to improve the mechanical properties of the cured product.

[0102] [Dental Material] The dental material of the present disclosure includes the hardenable composition of the present disclosure or a cured product of the hardenable composition of the present disclosure. A dental material of the present disclosure comprising the hardenable composition of the present disclosure is, for example, a composite resin for filling caries cavities. In this case, the objective can be achieved by filling a cavity in the oral cavity with the composite resin for filling caries cavities and then photocuring it using a known light irradiation device. The dental material of the present disclosure comprising the hardenable composition of the present disclosure may also be a composite resin for crowns. In this case, the composite resin for crowns can be processed into an appropriate shape, photocured using a known light irradiation device, and then heat-treated under specified conditions to obtain a desired dental crown material.

[0103] The hardenable composition of the present disclosure may be used in dental treatment. A dental treatment method using the hardenable composition of the present disclosure (or a dental material containing this hardenable composition) may include a step of polymerizing the hardenable composition of the present disclosure in the oral cavity to obtain a cured product. The hardenable composition of the present disclosure (or a dental material containing this hardenable composition) when used to obtain a cured product by polymerization in the oral cavity is suitable as, for example, a dental adhesive resin cement, a composite resin for filling and restoring, etc.

[0104] A dental treatment method using the hardenable composition of the present disclosure (or a dental material containing this hardenable composition) 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 of the present disclosure outside the oral cavity to obtain a cured product may be a step of polymerizing the hardenable composition of the present disclosure in a casting mold to obtain a cured product. The cured product obtained by polymerizing the hardenable composition of the present disclosure outside the oral cavity may be processed as necessary, and the processed cured product may be applied into the oral cavity. The cured product obtained by polymerizing the hardenable composition of the present disclosure outside the oral cavity (or a dental material containing this cured product) is suitable for use as, for example, a resin block for CAD / CAM, a temporary crown, an artificial tooth, etc.

[0105] The hardenable composition and dental material of the present disclosure can be preferably used as, for example, a dental restorative material, a denture base resin, a denture base lining material, an impression material, a luting material (e.g., resin cement, resin-added glass ionomer cement), a dental adhesive (e.g., orthodontic adhesive, cavity application adhesive), a fissure sealant, a resin block for CAD / CAM, a temporary crown, an artificial tooth material, etc. Dental restorative materials can be classified by application range into composite resins for crowns, composite resins for filling caries cavities, composite resins for core construction, composite resins for filling restorations, etc. Of these, the hardenable composition and dental material of the present disclosure are particularly suitable for dental restorative materials such as composite resins.

[0106] Examples of the present disclosure are shown below, but the present disclosure is not limited to the following examples. Hereinafter, the term "monomer" simply refers to a (meth)acrylate compound (specifically, a thiourethane (meth)acrylate compound or a comparative (meth)acrylate compound) unless otherwise specified.

[0107] The abbreviations for the compounds used in the examples are shown below. <Isocyanate Compounds (D)> XDI: m-xylylene diisocyanate (the above-mentioned compound (D1)) TMXDI: 1,3-tetramethylxylylene diisocyanate (the above-mentioned compound (D3)) NBDI: a mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (the above-mentioned compound (D2)) TMHDI: trimethylhexamethylene diisocyanate (a mixture of a 2,2,4-substituted product (the above-mentioned compound (D6)) and a 2,4,4-substituted product (the above-mentioned compound (D7))) <Thiol Compounds (B)> T1: 3,6-dioxa-1,8-octanedithiol (the above-mentioned compound (B1-2)) T2: 1,4-butanedithiol (the above-mentioned compound (B1-1)) T3: 1,8-octanedithiol (the above-mentioned compound (B1-1)) T4: ethylene glycol bis(3-mercaptopropionate) (the above-mentioned compound (B1-4)) T5: 3,7-dithia-1,9-nonanedithiol (the above-mentioned compound (B1-3)) <(meth)acrylate compound (C)> 4HBA: 4-hydroxybutyl acrylate 2HBMA: 2-hydroxybutyl methacrylate HPMA: hydroxypropyl methacrylate HPA: hydroxypropyl acrylate HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate <(meth)acrylate compound> TEGDMA: triethylene glycol dimethacrylate UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate <Urethanization catalyst> DiBTSn: dibutyltin dilaurate <Polymerization initiator> CQ: (±)-camphorquinone BEDB: 2-butoxyethyl 4-(dimethylamino)benzoate Luperox 531M80 (1,1-di(t-amylperoxy)cyclohexane; manufactured by Arkema Yoshitomi Co., Ltd.) <Polymerization inhibitor> BHT: 2,6-di-tert-butyl-p-cresol

[0108] <Preparation of Test Pieces for Bending Tests by Photopolymerization> TEGDMA (4 parts by mass) was added to 6 parts by mass of each monomer to be evaluated (specifically, each monomer shown in the "6 (parts by mass)" column in Tables 3 and 4). The mixture was stirred at 50°C until homogeneous, yielding a monomer composition. CQ (0.03 parts by mass) and BEDB (0.03 parts by mass) were added to the resulting monomer composition and stirred at room temperature until homogeneous, yielding a curable composition for photopolymerization. The resulting curable composition for photopolymerization was placed in a 2 mm x 2 mm x 25 mm stainless steel mold and irradiated with light for 3 minutes on each side, for a total of 6 minutes on both sides, using a visible light irradiation device (α Light V, manufactured by Morita Corporation). This photopolymerized the monomers in the curable composition, photocuring the curable composition, and yielding a cured product. The resulting cured product was immersed in distilled water in a sealed sample bottle and maintained in this state at 37°C for 24 hours, yielding a test piece for bending tests.

[0109] <Preparation of Test Pieces for Bending Test by Thermal Polymerization> TEGDMA (10 parts by mass) was added to 30 parts by mass of each monomer to be evaluated (specifically, each monomer shown in the "30 (parts by mass)" column in Table 5), and the mixture was stirred at 50°C until homogeneous, to obtain a monomer composition. Luperox 531M80 (0.32 parts by mass) was added to the obtained monomer composition, and the mixture was stirred at room temperature until homogeneous. 60 parts by mass of silica glass (GM8235, SCHOTT) as a filler was further added to the mixture, and the mixture was stirred and defoamed using a stirring defoamer (Mazerustar, manufactured by Kurabo Industries, Ltd.), to obtain a curable composition for thermal polymerization. The obtained curable composition for thermal polymerization was placed in a screw cap bottle (FC screw cap bottle No. 7) and thermally cured using a small environmental tester (SU-222, manufactured by ESPEC Corporation) for 40 hours at a maximum temperature of 115°C by thermally polymerizing the monomers in the curable composition, thereby obtaining a cured product A. The obtained cured product A was removed from the screw cap bottle and further cured using the small environmental tester at 130°C for 2 hours to obtain a cured product B. A 2 mm x 2 mm x 25 mm test piece was cut from the obtained cured product B using a precision cutting machine (Preciso CL-40, manufactured by Sankei Corporation). The obtained test piece was placed in the small environmental tester and heat-treated at 130°C for 1 hour. The test piece was then immersed in distilled water in a sealed sample bottle and maintained in this state at 37°C for 24 hours to obtain a test piece for a bending test.

[0110] <Bending test> The bending test specimens obtained by either the above "Preparation of bending test specimens by photopolymerization" or the above "Preparation of bending test specimens by thermal polymerization" were subjected to a three-point bending test using a testing machine (Shimadzu Autograph EZ-S) under conditions of a support distance of 20 mm and a crosshead speed of 1 mm / min, and the maximum stress (MPa) and elastic modulus (MPa) were measured.

[0111] <Production of Thiourethane (Meth)acrylate Compounds> Monomers 1 to 22, which are specific examples of the thiourethane (meth)acrylate compounds of the present disclosure, were produced as follows.

[0112] (Production of Monomer 1) DiBTSn (0.1 parts by mass), TMXDI (23.40 parts by mass) as the isocyanate compound (D), BHT (0.05 parts by mass), and T1 (1.75 parts by mass) as the thiol compound (B) were charged into a 100 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and dissolved to form a homogeneous solution. The resulting homogeneous solution was reacted at 80 ° C for 4 hours to obtain a solution containing an intermediate. The resulting solution was heated to 90 ° C, and 4HBA (24.86 parts by mass) as the (meth)acrylate compound (C) was added dropwise thereto over 1 hour. Since the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled so that it remained below 90 ° C. After the entire amount of 4HBA (24.86 parts by mass) was added dropwise, the reaction temperature was maintained at 90 ° C, and the reaction was carried out for 10 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point of the reaction. The product was discharged from the reactor to obtain a composition (50 g) containing Monomer 1, a specific example of the thiourethane (meth)acrylate compound of the present disclosure. Table 1 shows the types and amounts of the isocyanate compound (D), thiol compound (B), and (meth)acrylate compound (C), as well as the molar ratio of the amount of mercapto groups (SH groups) in the amount of thiol compound (B) charged to the amount of isocyanate groups (NCO groups) in the amount of isocyanate compound (D) charged (hereinafter also referred to as "SH / NCO").

[0113] (Monomers 2 to 22) Compositions (50 g) containing any of Monomers 2 to 22 were obtained in the same manner as in the production of Monomer 1, except that the types and amounts of the isocyanate compound (D), the thiol compound (B), and the (meth)acrylate compound (C) were changed as shown in Tables 1 and 2.

[0114]

[0115]

[0116] 1 to 22 show the IR spectra (i.e., infrared absorption spectra) of Monomers 1 to 22, respectively. These IR spectra were measured at a temperature of 20°C. From these IR spectra, it was confirmed that all of Monomers 1 to 22 contain the compound represented by the above formula (A1). In the compound represented by formula (A1) contained in each of Monomers 1 to 22, R １Ａ is a residue obtained by removing two mercapto groups from a thiol (B) shown in Tables 1 and 2, and R ２Ａ is a residue obtained by removing two isocyanate groups from the isocyanate (D) shown in Tables 1 and 2, and R ３Ａ is a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from the (meth)acrylate (C) shown in Tables 1 and 2. Among Monomers 1 to 22, R ４Ａ is a hydrogen atom, and R in the monomer where (meth)acrylate (C) is a methacrylate ４Ａ is a methyl group.

[0117] 1 to 22 show the infrared absorption spectra of Monomers 1 to 22, respectively. These infrared absorption spectra were measured at a temperature of 20°C.

[0118] [Comparative Example 1, Examples 1 to 16] Using each monomer shown in the "6 (parts by mass)" column in Tables 3 and 4 below, a curable composition for photopolymerization and a test piece for a bending test were prepared according to the above-mentioned "Preparation of test piece for bending test by photopolymerization." The above-mentioned "Bending test" was carried out using the obtained test piece for bending test. The results are shown in Tables 3 and 4.

[0119]

[0120]

[0121] As shown in Tables 3 and 4, the cured products obtained by photopolymerization (i.e., photocuring) using the curable compositions for photopolymerization containing each of the monomers in Examples 1 to 16 were superior in bending strength (specifically, maximum stress and elastic modulus) compared to the cured products obtained by photopolymerization (i.e., photocuring) using the curable compositions for photopolymerization containing UDMA.

[0122] [Comparative Example 101, Examples 101 to 109] Using each monomer shown in the "30 (parts by mass)" column in Table 5, a curable composition for thermal polymerization and a test piece for a bending test were prepared according to the above-mentioned "Preparation of test piece for bending test by thermal polymerization." The above-mentioned "Bending test" was carried out using the obtained test piece for bending test. The results are shown in Table 5.

[0123]

[0124] As shown in Table 5, the cured products obtained by thermal polymerization (i.e., thermosetting) using the curable compositions for thermal polymerization containing the monomers in Examples 101 to 109 were superior in bending strength (specifically, maximum stress and elastic modulus) compared to the cured products obtained by thermal polymerization (i.e., thermosetting) using the curable compositions for thermal polymerization containing UDMA.

[0125] The disclosure of Japanese Patent Application No. 2024-015856, filed on February 5, 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. A thiourethane (meth)acrylate compound containing two bonds represented by the following formula (X), two urethane bonds, and two (meth)acryloyl groups: [In formula (X), each of the two * marks represents a bonding position.] 2. The thiourethane (meth)acrylate compound according to claim 1, which is a reaction product of a thiol compound (B) containing two mercapto groups, a (meth)acrylate compound (C) containing one hydroxy group and one (meth)acryloyloxy group, and an isocyanate compound (D) containing two isocyanate groups.

3. The thiourethane (meth)acrylate compound according to claim 1, which is a compound represented by the following formula (A1): [In formula (A1), R １Ａ is a residue obtained by removing two mercapto groups from a thiol compound (B) containing two mercapto groups, and R ２Ａ is a residue obtained by removing two isocyanate groups from an isocyanate compound (D) containing two isocyanate groups, and R ３Ａ is a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from a (meth)acrylate compound (C) containing one hydroxy group and one (meth)acryloyloxy group, and R ４Ａ is a hydrogen atom or a methyl group, and two R ２Ａ may be the same or different, and two R ３Ａ may be the same or different, and two R ４Ａ may be the same or different.

4. The thiourethane (meth)acrylate compound according to claim 3, wherein the isocyanate compound (D) includes a compound represented by any one of the following formulas (D1) to (D8):

5. The thiourethane (meth)acrylate compound according to claim 3, wherein the thiol compound (B) includes a compound represented by the following formula (B1): [In formula (B1), R Ｂ is a divalent organic group having 1 to 20 carbon atoms.

6. The thiourethane (meth)acrylate compound according to claim 3, wherein the (meth)acrylate compound (C) includes a compound represented by the following formula (C1): [In formula (C1), R １Ｃ is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R ２Ｃ is a hydrogen atom or a methyl group.

7. A monomer composition comprising the thiourethane (meth)acrylate compound according to any one of claims 1 to 6.

8. The monomer composition according to claim 7, which is used as a dental material.

9. A curable composition comprising the thiourethane (meth)acrylate compound according to any one of claims 1 to 6 and a polymerization initiator.

10. A dental material comprising the hardenable composition according to claim 9 or a hardened product of said hardenable composition.

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