Compound, monomer composition, curable composition, and cured product

Abstract

A compound containing a urethane bond, a thiourethane bond, and an allyl group.

Description

Compound, monomer composition, curable composition, and cured product

[0001] The present disclosure relates to compounds, monomer compositions, curable compositions, and cured products.

[0002] In recent years, in relation to dental products such as dental prostheses and instruments used in the oral cavity, a method for producing three-dimensional objects such as dental products by stereolithography using a 3D printer has become known from the viewpoint of manufacturing efficiency (see, for example, Patent Document 1).

[0003] Patent Document 1: Patent No. 4160311

[0004] While mechanical strength such as toughness is sometimes required for cured products such as stereolithography using a 3D printer, if the viscosity of the curable composition during curing is too high, operability during curing may decrease. On the other hand, low-viscosity monomers suitable for suppressing an increase in the viscosity of the curable composition (for example, the compound of Comparative Example 1 described below) were sometimes insufficient in terms of the toughness that could be imparted to the cured product.

[0005] An object of one embodiment of the present disclosure is to provide a compound and a monomer composition that can impart excellent toughness to a cured product and are suitable for suppressing an increase in viscosity of a curable composition, a curable composition containing the compound, and a cured product of the curable composition.

[0006] Specific means for solving the above problems are as follows: <1> A compound containing a urethane bond, a thiourethane bond, and an allyl group. <2> The compound according to <1>, further containing a (meth)acryloyl group. <3> The compound according to <1> or <2>, having a molecular weight of 2,000 or less. <4> The compound according to any one of <1> to <3>, which is a reaction product of a thiol compound (B) containing two or more mercapto groups, an iso(thio)cyanate compound (C) containing two or more iso(thio)cyanato groups, and an allyl compound (D) containing a hydroxy group and an allyl group. <5> The compound according to any one of <1> to <4>, which is a reaction product of a thiol compound (B) containing two or more mercapto groups, an iso(thio)cyanate compound (C) containing two or more iso(thio)cyanato groups, an allyl compound (D) containing a hydroxy group and an allyl group, and a (meth)acrylate compound (E) containing a hydroxy group and a (meth)acryloyloxy group. <6> The compound according to any one of <1> to <5>, which is a compound represented by the following formula (1):

[0007]

[0008] In formula (1), X is m represented by formula (X1). Ｙ +n Ｙ is a valent group, R ３ is a residue obtained by removing one hydroxy group and one allyl group from an allyl compound (D) containing a hydroxy group and an allyl group, or a single bond, and R ４ is a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from a (meth)acrylate compound (E) containing a hydroxy group and a (meth)acryloyloxy group, and R ５ is a hydroxyl atom or a methyl group, R ６ is an oxygen atom or a sulfur atom, m Ｙ is an integer from 1 to 4, and n Ｙ is an integer from 0 to 3, and m Ｙ +n Ｙ is an integer of 2 to 4. In formula (X1), R １is a residue obtained by removing all mercapto groups from a thiol compound (B) containing 2 to 4 mercapto groups, and R ２ is a residue obtained by removing all iso(thio)cyanato groups from an iso(thio)cyanato compound (C) containing two iso(thio)cyanato groups, and n Ｘ is m in formula (1) Ｙ +n Ｙ and * indicates a bonding position. ６ In formula (1), R ２ If there are multiple R ２ In formula (1), R ３ If there are multiple R ３ In formula (1), R ４ If there are multiple R ４ In formula (1), R ５ If there are multiple R ５ may be the same or different.

[0009] <7> The compound according to any one of <4> to <6>, wherein the thiol compound (B) includes a compound represented by any one of the following formulas (B1) to (B16):

[0010]

[0011] In formula (B16), R Ｂ is a divalent organic group having 1 to 20 carbon atoms.

[0012] <8> The compound according to any one of <4> to <7>, wherein the isocyanate compound (C) includes a compound represented by any one of the following formulas (C1) to (C8):

[0013]

[0014] <9> The compound according to any one of <4> to <8>, wherein the allyl compound (D) includes a compound represented by any one of the following formulas (D1) to (D4):

[0015]

[0016] <10> The compound according to any one of <4> to <9>, wherein the (meth)acrylate compound (E) includes a compound represented by the following formula (E1):

[0017]

[0018] In formula (E1), R Ｅ１ is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R Ｅ２ is a hydrogen atom or a methyl group.

[0019] <11> A monomer composition comprising the compound according to any one of <1> to <10>. <12> The monomer composition according to <11>, used in the production of a dental product. <13> A hardenable composition comprising the monomer composition according to <11> or <12> and a polymerization initiator. <14> The hardenable composition according to <13>, used in the production of a dental product. <15> A cured product of the hardenable composition according to <13> or <14>.

[0020] According to one aspect of the present disclosure, there are provided a compound and a monomer composition that can impart excellent toughness to a cured product and are suitable for suppressing an increase in viscosity of a curable composition, a curable composition containing the compound, and a cured product of the curable composition.

[0021] FIG. 1 shows an infrared absorption spectrum of compound (A) of Example 1, which is a specific example of a compound of the present disclosure. FIG. 2 shows an infrared absorption spectrum of compound (A) of Example 2, which is a specific example of a compound of the present disclosure. FIG. 3 shows an infrared absorption spectrum of compound (A) of Example 3, which is a specific example of a compound of the present disclosure. FIG. 4 shows an infrared absorption spectrum of compound (A) of Example 4, which is a specific example of a compound of the present disclosure. FIG. 5 shows an infrared absorption spectrum of compound (A) of Example 5, which is a specific example of a compound of the present disclosure. FIG. 6 shows an infrared absorption spectrum of compound (A) of Example 6, which is a specific example of a compound of the present disclosure. FIG. 7 shows an infrared absorption spectrum of compound (A) of Example 7, which is a specific example of a compound of the present disclosure. FIG. 8 shows an infrared absorption spectrum of compound (A) of Example 9, which is a specific example of a compound of the present disclosure. FIG. 10 shows an infrared absorption spectrum of compound (A) of Example 10, which is a specific example of a compound of the present disclosure. FIG. 11 shows an infrared absorption spectrum of compound (A) of Example 11, which is a specific example of a compound of the present disclosure. FIG. 12 shows an infrared absorption spectrum of compound (A) of Example 12, which is a specific example of a compound of the present disclosure. FIG. 1 is an infrared absorption spectrum of compound (A) of Example 13, which is a specific example of a compound of the present disclosure. FIG. 2 is an infrared absorption spectrum of compound (A) of Example 14, which is a specific example of a compound of the present disclosure. FIG. 3 is an infrared absorption spectrum of compound (A) of Example 15, which is a specific example of a compound of the present disclosure. FIG. 4 is an infrared absorption spectrum of compound (A) of Example 16, which is a specific example of a compound of the present disclosure. FIG. 5 is an infrared absorption spectrum of compound (A) of Example 17, which is a specific example of a compound of the present disclosure. FIG. 6 is an infrared absorption spectrum of compound (A) of Example 18, which is a specific example of a compound of the present disclosure. FIG. 7 is an infrared absorption spectrum of compound (A) of Example 19, which is a specific example of a compound of the present disclosure. FIG. 8 is an infrared absorption spectrum of compound (A) of Example 20, which is a specific example of a compound of the present disclosure.

[0022] 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 multiple substances corresponding to each component exist, the amount of each component refers to the total amount of the multiple substances unless otherwise specified. In this disclosure, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group, "(meth)acrylate" means an acrylate or a methacrylate, "iso(thio)cyanato group" means an isocyanato group or an isothiocyanato group, and "iso(thio)cyanate compound" means an isocyanate compound or an isothiocyanate compound. In the present disclosure, the term "urethane bond" includes, for example, a bond formed by a reaction between an isocyanato group of an isocyanate compound and a hydroxy group of an allyl compound (D) or a (meth)acrylate compound (E), and a bond formed by a reaction between an isocyanato group of an isothiocyanate compound and a hydroxy group of an allyl compound (D) or a (meth)acrylate compound (E). In the present disclosure, the term "thiourethane bond" includes, for example, a bond formed by a reaction between an isocyanato group of an isocyanate compound and a mercapto group of a thiol compound (B), and a bond formed by a reaction between an isocyanato group of an isocyanate compound and a mercapto group of a thiol compound (B).

[0023] Specifically, the urethane bond in the present disclosure includes the following two (in the following formula, * indicates the bonding position):

[0024]

[0025] Specifically, the thiourethane bond in the present disclosure includes the following two (in the following formula, * indicates the bonding position):

[0026]

[0027] [Compound (A)] The compound of the present disclosure (hereinafter sometimes referred to as "compound (A)") contains a urethane bond, a thiourethane bond, and an allyl group. Compound (A) can impart excellent toughness to the cured product and is suitable for suppressing an increase in viscosity of the curable composition. In other words, the cured product of the curable composition containing compound (A) has excellent toughness, and the curable composition containing compound (A) has a reduced viscosity.

[0028] The effect of improving the toughness of the cured product is believed to be an effect achieved by the combination of the urethane bond, the thiourethane bond, and the allyl group in compound (A), and the effect of reducing the viscosity of the curable composition is believed to be an effect achieved by the allyl group.

[0029] The compound (A) preferably further contains a (meth)acryloyl group, which further improves the toughness of the cured product.

[0030] The molecular weight of the compound (A) is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, and still more preferably 1800 or less, thereby further reducing the viscosity of the curable composition.

[0031] The lower limit of the molecular weight of the compound (A) is not particularly limited as long as the compound (A) contains a urethane bond, a thiourethane bond, and an allyl group. The lower limit of the molecular weight of the compound (A) is, for example, 500.

[0032] Compound (A) is preferably a reaction product of a thiol compound (B) containing two or more mercapto groups, an iso(thio)cyanate compound (C) containing two or more iso(thio)cyanato groups, and an allyl compound (D) containing a hydroxy group and an allyl group. In this case, a thiourethane bond is formed by the reaction of the mercapto group in the thiol compound (B) with the iso(thio)cyanato group in the iso(thio)cyanate compound (C), and a urethane bond is formed by the reaction of the hydroxy group in the allyl compound (D) with the iso(thio)cyanato group in the iso(thio)cyanate compound (C). The allyl group in the allyl compound (D) remains in the reaction product, compound (A). As a result, the reaction product, compound (A), contains a urethane bond, a thiourethane bond, and an allyl group.

[0033] Compound (A) is more preferably a reaction product of a thiol compound (B) containing two or more mercapto groups, an iso(thio)cyanate compound (C) containing two or more iso(thio)cyanato groups, an allyl compound (D) containing a hydroxy group and an allyl group, and a (meth)acrylate compound (E) containing a hydroxy group and a (meth)acryloyloxy group. In this case, a thiourethane bond is formed by the reaction of the mercapto group in the thiol compound (B) with the iso(thio)cyanato group in the iso(thio)cyanate compound (C), and a urethane bond is formed by the reaction of the hydroxy group in the allyl compound (D) with the iso(thio)cyanato group in the iso(thio)cyanate compound (C). A urethane bond can also be formed by the reaction of the hydroxy group in the (meth)acrylate compound (E) with the iso(thio)cyanato group in the iso(thio)cyanate compound (C). The allyl group in the allyl compound (D) and the (meth)acryloyloxy group in the (meth)acrylate compound (E) remain intact in the reaction product, compound (A). As a result, the reaction product, compound (A), contains a urethane bond, a thiourethane bond, an allyl group, and a (meth)acryloyloxy group.

[0034] The compound (A) is preferably a compound represented by the following formula (1):

[0035]

[0036] In formula (1), X is m represented by formula (X1). Ｙ +n Ｙ is a valent group, R ３ is a residue obtained by removing one hydroxy group and one allyl group from an allyl compound (D) containing a hydroxy group and an allyl group, or a single bond, and R ４ is a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from a (meth)acrylate compound (E) containing a hydroxy group and a (meth)acryloyloxy group, and R ５ is a hydroxyl atom or a methyl group, R ６ is an oxygen atom or a sulfur atom, m Ｙ is an integer from 1 to 4, and n Ｙ is an integer from 0 to 3, and m Ｙ +n Ｙ is an integer of 2 to 4. In formula (X1), R １ is a residue obtained by removing all mercapto groups from a thiol compound (B) containing 2 to 4 mercapto groups, and R ２ is a residue obtained by removing all iso(thio)cyanato groups from an iso(thio)cyanato compound (C) containing two iso(thio)cyanato groups, and n Ｘ is m in formula (1) Ｙ +n Ｙ and * indicates a bonding position. ６ In formula (1), R ２ If there are multiple R ２ In formula (1), R ３ If there are multiple R ３ In formula (1), R ４ If there are multiple R ４ In formula (1), R ５If there are multiple R ５ may be the same or different.

[0037] Preferred embodiments of raw materials (i.e., thiol compound (B), iso(thio)cyanate compound (C), allyl compound (D), and (meth)acrylate compound (E)) for producing compound (A) (e.g., the above-mentioned reaction product and the compound represented by formula (1)) are shown below.

[0038] <Thiol Compound (B)> The thiol compound (B) is a compound containing two or more mercapto groups. The number of mercapto groups contained in the thiol compound (B) is preferably 2 to 4. When the number of mercapto groups contained in the thiol compound (B) is 4 or less, the viscosity described above (i.e., the viscosity of the stereolithography monomer composition alone according to the present disclosure, or the viscosity of the stereolithography photocurable composition containing the stereolithography monomer composition according to the present disclosure and a photopolymerization initiator) can be further reduced.

[0039] The molecular weight of the thiol compound (B) is preferably 1,000 or less, more preferably 600 or less.

[0040] The thiol compound (B) preferably includes a compound represented by any one of the following formulas (B1) to (B16):

[0041]

[0042] In formula (B16), R Ｂ is a divalent organic group having 1 to 20 carbon atoms.

[0043] The compound represented by formula (B16) preferably contains a thiol compound represented by any one of the following formulae (B16-1) to (B16-5).

[0044]

[0045] In formula (B16-1), 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 (B16-4), n is an integer of 1 to 10.

[0046] The total proportion of the thiol compounds represented by any one of Formulas (B1) to (B16) 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] <Iso(thio)cyanate compound (C)> The iso(thio)cyanate compound (C) is a compound containing two or more isocyanato groups. The iso(thio)cyanate compound (C) preferably includes a compound containing two isocyanato groups (i.e., a diisocyanate compound).

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

[0049] The isocyanate compound (C) preferably includes a compound containing two isocyanato groups, and more preferably includes a compound represented by any one of the following formulas (C1) to (C8):

[0050]

[0051] The total proportion of the compounds represented by any one of Formulas (C1) to (C8) in the iso(thio)cyanate 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.

[0052] <Allyl Compound (D)> The allyl compound (D) is a compound containing a hydroxy group and an allyl group. The number of allyl groups in the allyl compound (D) is one or more, preferably one to three. The allyl group in the allyl compound (D) is preferably bonded to an oxygen atom to form an allyloxy group. That is, the allyl compound (D) preferably contains a hydroxy group and an allyloxy group. The number of allyloxy groups in the allyl compound (D) is one or more, preferably one to three. The number of hydroxy groups in the allyl compound (D) is one or more, preferably one.

[0053] The molecular weight of the allyl compound (D) is preferably 1,000 or less, more preferably 500 or less, and even more preferably 400 or less.

[0054] The allyl compound (D) preferably includes a compound containing one hydroxy group and one to three allyl groups, more preferably includes a compound containing one hydroxy group and one to three allyloxy groups, and more preferably includes a compound represented by any of the following formulas (D1) to (D4):

[0055]

[0056] The total proportion of the compounds represented by any one of Formulas (D1) to (D4) in the allyl 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.

[0057] <(Meth)acrylate Compound (E)> The (meth)acrylate compound (E) is a compound containing a hydroxy group and a (meth)acryloyloxy group. The number of hydroxy groups in the (meth)acrylate compound (E) is one or more, preferably one. The number of (meth)acryloyloxy groups in the (meth)acrylate compound (E) is one or more, preferably one.

[0058] The molecular weight of the (meth)acrylate compound (E) is preferably 1,000 or less, more preferably 500 or less, and even more preferably 400 or less.

[0059] The (meth)acrylate compound (E) preferably includes a compound containing one hydroxy group and one (meth)acryloyloxy group, and more preferably includes a compound represented by the following formula (E1):

[0060]

[0061] In formula (E1), R Ｅ１ is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R Ｅ２ is a hydrogen atom or a methyl group.

[0062] R Ｅ１ The organic group represented by R contains one hydroxy group and may contain a hydrocarbon group. Ｅ１ The organic group represented by the formula (I) may further contain an ester bond, an ether bond, a sulfide bond, or the like.

[0063] The proportion of the compound represented by formula (E1) in the (meth)acrylate compound (E) 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.

[0064] Examples of the (meth)acrylate compound (E) 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.

[0065] The (meth)acrylate compound (E) 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. The proportion of these compounds in the (meth)acrylate compound (E) 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.

[0066] <An example of a method for producing compound (A) (production method X)> Hereinafter, an example of a method for producing compound (A) (hereinafter also referred to as "production method X") will be shown.

[0067] Production method X includes a reaction step of reacting the above-mentioned thiol compound (B), the above-mentioned iso(thio)cyanate compound (C), the above-mentioned allyl compound (D), and (optionally, the (meth)acrylate compound (E)) to produce compound (A). Production method X may include other steps as required. According to production method X, compound (A) (e.g., a compound represented by formula (1)) is produced as a reaction product of the above-mentioned thiol compound (B), the above-mentioned iso(thio)cyanate compound (C), the above-mentioned allyl compound (D), and (optionally, the (meth)acrylate compound (E)). Production method X may include other steps as required.

[0068] 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.

[0069] (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.

[0070] 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 iso(thio)cyanate compound (C), the allyl compound (D), and the (meth)acrylate compound (E).

[0071] 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.

[0072] 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.

[0073] 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).

[0074] 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 iso(thio)cyanate compound (C), the allyl compound (D), and the (meth)acrylate compound (E).

[0075] [Monomer Composition] The monomer composition of the present disclosure contains compound (A) (i.e., the compound of the present disclosure). Accordingly, the monomer composition of the present disclosure exhibits the same effects as those of compound (A) (i.e., the compound of the present disclosure) (i.e., the effects of reducing the viscosity of the curable composition and improving the toughness of a cured product of the curable composition).

[0076] The content of 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 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 compound (A) in a content of 90% by mass or more and impurities.

[0077] 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 used for producing dental products. Specific examples of dental products will be described later.

[0078] [Curable Composition] The curable composition of the present disclosure contains the monomer composition of the present disclosure and a polymerization initiator. The curable composition of the present disclosure may also contain other components.

[0079] The curable composition of the present disclosure contains the monomer composition of the present disclosure, and therefore exhibits the same effects as those of the monomer composition of the present disclosure (i.e., the effects of reducing the viscosity of the curable composition and improving the toughness of a cured product of the curable composition).

[0080] The proportion of the monomer composition of the present disclosure in the curable 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.

[0081] The curable composition of the present disclosure may be a photocurable composition or a heat-curable composition, but is preferably a photocurable composition.

[0082] <Polymerization initiator> The curable composition of the present disclosure contains at least one polymerization initiator. The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, but is preferably a photopolymerization initiator. The curable composition of the present disclosure in an embodiment that is a photocurable composition contains a photopolymerization initiator as the polymerization initiator.

[0083] The photopolymerization initiator may be, for example, a general photopolymerization initiator used in the field of stereolithography, such as an alkylphenone compound, an acylphosphine oxide compound, a titanocene compound, an oxime ester compound, a benzoin compound, an acetophenone compound, a benzophenone compound, a thioxanthone compound, an α-acyloxime ester compound, a phenyl glyoxylate compound, a benzyl compound, an azo compound, a diphenyl sulfide compound, an iron phthalocyanine compound, a benzoin ether compound, or an anthraquinone compound.

[0084] The photopolymerization initiator preferably contains at least one selected from the group consisting of alkylphenone compounds and acylphosphine oxide compounds. From the viewpoint of further improving the modeling accuracy of the stereolithography object, the photopolymerization initiator more preferably contains at least one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-hydroxy-cyclohexyl phenyl ketone, phenylglyoxylic acid methyl ester, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1,2-octanedione, and 1-{4-(phenylthio)-, 2-(O-benzoyloxime)}.

[0085] The amount of the polymerization initiator contained in the curable composition of the present disclosure is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, and even more preferably 1 part by mass to 5 parts by mass, relative to 100 parts by mass of the curable composition.

[0086] <(Meth)acrylate Compound (F)> The curable composition of the present disclosure may contain a (meth)acrylate compound (F) that is a (meth)acrylate compound other than the (meth)acrylate compound (E).

[0087] Examples of the (meth)acrylate compound (F) 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, polyethylene glycol Examples of the (meth)acrylate compound (F) include cholesteryl 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 (note: a compound known as "urethane dimethacrylate (UDMA)"). One type of (meth)acrylate compound (F) may be used alone, or two or more types may be used in combination.

[0088] For example, in order to adjust the viscosity of the curable composition to a low level, a viscosity-adjusting monomer such as triethylene glycol dimethacrylate may be used as the (meth)acrylate compound (F). In this case, the viscosity-adjusting monomer as the (meth)acrylate compound (F) and the compound (A) may be used in a mass ratio of 1:0.8 to 1.2.

[0089] When the curable composition of the present disclosure contains a (meth)acrylate compound (F), the proportion of the (meth)acrylate compound (F) in the curable 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 curable composition of the present disclosure contains a (meth)acrylate compound (F), the proportion of the compound (A) in the curable 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.

[0090] <Other Components> The curable composition of the present disclosure may contain other components in addition to the above-described components, as necessary. Examples of other components include a colorant, an inorganic filler, a modifier, a stabilizer, an antioxidant, and a solvent.

[0091] From the viewpoint of further improving the modeling accuracy of the cured product, it is preferable that the curable composition for stereolithography according to the present disclosure does not contain an inorganic filler (e.g., silica, barium borosilicate glass, etc.; the same applies hereinafter), or, if it contains an inorganic filler, the content of the inorganic filler relative to the total amount of the curable composition for stereolithography is 10% by mass or less (more preferably 5% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less).

[0092] <Preferred Viscosity of Curable Composition> The curable composition of the present disclosure preferably has a viscosity (hereinafter also simply referred to as "viscosity") measured using an E-type viscometer at 25°C and 50 rpm of 5 mPa s or more and less than 190 mPa s. Here, rpm means revolutions per minute. When the viscosity is 5 mPa s or more and less than 190 mPa s, the curable composition has excellent handleability.

[0093]

[0033] The curable composition of the present disclosure may be used for the production of dental products, preferably for the purpose of reducing the viscosity of the curable composition and improving the toughness of the cured product.

[0094] Dental products include dentures (i.e., artificial teeth), denture bases, dental prostheses, dental restorative materials, medical instruments used in the oral cavity, dental models, models for lost-loss casting, etc. Dental prostheses include inlays, crowns, bridges, temporary crowns, temporary bridges, etc. Medical instruments used in the oral cavity include mouthpieces, mouthguards, orthodontic appliances, occlusal splints, impression-taking trays, surgical guides, etc. Dental models include tooth and jaw models, etc.

[0095] 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.

[0096] 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.

[0097] [Cured Product] The cured product of the present disclosure is a cured product of the curable composition of the present disclosure described above. The cured product of the present disclosure is obtained by curing the curable composition of the present disclosure by polymerizing the monomer (i.e., compound (A)) in the curable composition of the present disclosure by light irradiation or heat. The cured product of the present disclosure can be produced using the curable composition of the present disclosure, which has excellent toughness and reduced viscosity.

[0098] As a method for obtaining the cured product of the present disclosure, i.e., a method for curing the curable composition of the present disclosure (specifically, a method for polymerizing the monomer (i.e., compound (A)) in the curable composition of the present disclosure by light irradiation or heat), a known method can be appropriately applied.

[0099] One method for obtaining a cured product of the present disclosure is stereolithography. A cured product obtained by stereolithography is hereinafter referred to as a stereolithography product. The curable composition of the present disclosure can be used, for example, in liquid tank type (e.g., DLP type or SLA type, preferably DLP type) stereolithography, inkjet type stereolithography, etc.

[0100] In liquid vat-type stereolithography, a portion of a photocurable composition for stereolithography (i.e., an uncured photocurable composition in a liquid state; the same applies hereinafter) contained in a liquid vat is cured by light irradiation to form a cured layer, and this process is repeated to stack cured layers, thereby obtaining a stereolithographic object. Liquid vat-type stereolithography differs from inkjet-type stereolithography, which uses inkjet nozzles, in that it uses a liquid vat. Liquid vat-type stereolithography is broadly divided into DLP (Digital Light Processing) stereolithography and SLA (Stereolithography) stereolithography. In the DLP method, planar light is irradiated onto the photocurable composition in the liquid vat. In the SLA method, laser light is scanned onto the photocurable composition in the liquid vat.

[0101] An example of DLP-based stereolithography uses a 3D printer (e.g., Kulzer's "Cara Print 4.0," Asiga's "Max UV," etc.) equipped with: a build table movable in the vertical direction; a tray (i.e., liquid tank) arranged below the build table (on the gravity side; the same applies below) that includes a light-transmitting portion and contains a photocurable composition; and a light source (e.g., an LED light source) arranged below the tray for irradiating the photocurable composition in the tray with planar light through the light-transmitting portion of the tray. In this example, first, a gap of one layer is formed between the build table and the tray, and this gap is filled with photocurable composition. Next, planar light is irradiated from below through the light-transmitting portion of the tray onto the photocurable composition filled in the gap, curing the irradiated area to form a first cured layer. Next, the gap between the build table and the tray is widened by the next layer, and the resulting space is filled with photocurable composition. Next, the photocurable composition that has filled the space is irradiated with light in the same manner as for curing the first layer to form a second cured layer. By repeating the above operation, cured layers are stacked to produce a three-dimensional object. In this example, the three-dimensional object may be further cured by further irradiating the produced three-dimensional object with light.

[0102] Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples. Hereinafter, the term "monomer" simply means a (meth)acrylate compound unless otherwise specified.

[0103] The abbreviations for the compounds used in this example are shown below. <Thiol Compounds (B)> T1: A mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (a mixture of compounds represented by the above formulas (B5) to (B7)) T2: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (a compound represented by the above formula (B10)) T3: 3,6-dioxa-1,8-octanedithiol (a compound represented by the above formula (B16) (more specifically, formula (B16-2))) T4: Ethylene glycol bis(3-mercaptopropionate) (a compound represented by the above formula (B16) (more specifically, formula (B16-4) (n=1)))

[0104] <Allyl Compounds (D)> EGMA: ethylene glycol monoallyl ether (compound represented by the above formula (D1)) <(Meth)acrylate Compounds (E)> HEA: 2-hydroxyethyl acrylate HPA: 2-hydroxypropyl acrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate <Isocyanate Compounds (C)> XDI: m-xylylene diisocyanate (compound represented by the above formula (C1)) TMXDI: 1,3-tetramethylxylylene diisocyanate (compound represented by the above formula (C3)) NBDI: mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (compound represented by the above formula (C2)) H6XDI: 1,3-bis(isocyanatomethyl)cyclohexane (compound represented by the above formula (C4)) <(meth)acrylate compound (F) (meth)acrylate compound other than the (meth)acrylate compound (E))> TEGDMA: triethylene glycol dimethacrylate <photopolymerization initiator> Omnirad 819: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, manufactured by IGM RESINS B.V. <reaction catalyst> DBTDL: dibutyltin dilaurate <polymerization inhibitor> BHT: dibutylhydroxytoluene

[0105] <Method for Evaluating Viscosity of Photocurable Composition> The viscosity of each photocurable composition in the examples and comparative examples was measured using a rheometer (Thermo Fisher Scientific HAAKE MARS 40) and a parallel plate jig with a diameter of 25 mm at a measurement temperature of 25°C and a rotation speed of 50 rpm. Based on the obtained viscosity, the viscosity of the photocurable composition was evaluated according to the following evaluation criteria.

[0106] Viscosity evaluation criteria: A: Viscosity is 5 mPa·s or more and less than 180 mPa·s; B: Viscosity is 180 mPa·s or more and less than 190 mPa·s; C: Viscosity is 190 mPa·s or more

[0107] <Evaluation of Toughness of Cured Products (Fracture Toughness Test)> Cured products were prepared using each of the photocurable compositions in the Examples and Comparative Examples, and the resulting cured products were subjected to a fracture toughness test. Based on the results, the toughness of the cured products was evaluated. Details are shown below. The compositions were printed using a 3D printer (Kulzer, Cara Print 4.0) with visible light at a wavelength of 405 nm and an illuminance of 14 mJ / cm. ２ The resulting molded object was irradiated with ultraviolet light having a wavelength of 365 nm at 10 J / cm. ２ The object was irradiated under the conditions of 100°C and fully cured to obtain a stereolithography object (i.e., a cured product). The obtained cured product (hereinafter referred to as "test piece") was notched in accordance with ISO20795-1:2008, and then stored in a thermostatic water bath at 37±1°C for 7 days±2 hours. The test piece was then removed from the thermostatic water bath, and a fracture toughness test was performed on the removed test piece using a bending test in accordance with ISO20795-1:2008 to determine the total work of fracture (J / m ２ ) was measured. Fracture toughness testing by bending test (i.e., measurement of total work of fracture) was carried out using a universal testing machine (manufactured by Intesco Co., Ltd.) at a penetration speed of 1.0±0.2 mm / min. The obtained total work of fracture value was evaluated according to the following evaluation criteria and used as an index of toughness of the cured product. In the following evaluation criteria, the cured product with the best toughness is ranked "AA".

[0108] AA: Total work of destruction is 80 J / m ２ A: Total work of destruction was 70 J / m ２ More than 80J / m ２ B: The total work of fracture was less than 60 J / m ２ 70J / m or more ２ C: The total work of fracture was less than 55 J / m ２ 60J / m or more ２ D: The total work of fracture was less than 55 J / m ２ It was less than.

[0109] Example 1 Synthesis of Compound (A) DBTDL (0.1 parts by mass), BHT (0.05 parts by mass), XDI (22.64 parts by mass; approximately 0.120 mol) as the isocyanate compound (C), and T1 (2.21 parts by mass; approximately 0.0060 mol) 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 EGMA (11.06 parts by mass; approximately 0.108 mol) as the allyl compound (D) was added dropwise thereto over 1 hour, followed by HPA (14.09 parts by mass; approximately 0.108 mol) as the (meth)acrylate compound (E) over 1 hour. During the dropwise addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled so that the temperature remained below 90°C. After the entire amount of HPA (14.09 parts by mass) was added dropwise, the reaction temperature was maintained at 90°C and the reaction was carried out for 10 hours. During this time, the progress of the reaction was tracked by HPLC analysis to confirm the end point of the reaction. The product was discharged from the reactor to obtain compound (A) (approximately 50 g) of Example 1.

[0110] <Production and Evaluation of Photocurable Composition> The obtained compound (A) (50 parts by mass), TEGDMA (50 parts by mass) as the (meth)acrylate compound (F), and Omnirad 819 (2 parts by mass) as a photopolymerization initiator were mixed to obtain a photocurable composition. The obtained photocurable composition was used to perform the viscosity evaluation and toughness evaluation described above. The results are shown in Table 1.

[0111] Examples 2 to 20, Comparative Examples 1 and 2 Compound (A) was obtained in the same manner as in Example 1, except that the types and amounts of compounds shown in Tables 1 to 3 were used as the thiol compound (B), the isocyanate compound (C), the allyl compound (D), and the (meth)acrylate compound (E), respectively, were obtained, and the same operation as in Example 1 was carried out using the obtained compound (A). The results are shown in Tables 1 to 3. In Comparative Examples 1 and 2 in Table 1, "-" means that the corresponding compound was not used.

[0112] 1 to 20 show the IR spectra (i.e., infrared absorption spectra) of the compounds (A) of Examples 1 to 20, respectively. These IR spectra were measured at a temperature of 20°C. From these IR spectra, it was confirmed that all of the compounds of Examples 1 to 20 contained a urethane bond, a thiourethane bond, an allyl group, and a (meth)acryloyloxy group.

[0113]

[0114]

[0115]

[0116] As shown in Tables 1 to 3, in each Example in which the raw materials for compound (A) included an iso(thio)cyanate compound (C) containing two or more iso(thio)cyanato groups, a thiol compound (B) containing two or more mercapto groups, and an allyl compound (D) containing a hydroxy group and an allyl group (i.e., the resulting compound (A) included a urethane bond, a thiourethane bond, and an allyl group), the viscosity of the photocurable composition was reduced and the toughness of the cured product of the photocurable composition was excellent. The results of the comparative examples compared to each Example were as follows. Comparative Example 1, in which the raw materials for compound (A) did not include the thiol compound (B) and the allyl compound (D) (i.e., the resulting compound (A) did not include a thiourethane bond or an allyl group), showed insufficient toughness in the cured product of the photocurable composition. Furthermore, Comparative Example 2, in which the raw materials for compound (A) did not include the allyl compound (D) (i.e., the resulting compound (A) did not include an allyl group), showed a high viscosity of the photocurable composition.

[0117] The disclosure of Japanese Patent Application No. 2024-048730, filed on March 25, 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 compound containing a urethane bond, a thiourethane bond, and an allyl group.

2. The compound of claim 1 further comprising a (meth)acryloyl group.

3. The compound of claim 1, having a molecular weight of 2000 or less.

4. The compound according to claim 1, which is a reaction product of a thiol compound (B) containing two or more mercapto groups, an iso(thio)cyanate compound (C) containing two or more iso(thio)cyanato groups, and an allyl compound (D) containing a hydroxy group and an allyl group.

5. The compound according to claim 1, which is a reaction product of a thiol compound (B) containing two or more mercapto groups, an iso(thio)cyanate compound (C) containing two or more iso(thio)cyanato groups, an allyl compound (D) containing a hydroxy group and an allyl group, and a (meth)acrylate compound (E) containing a hydroxy group and a (meth)acryloyloxy group.

6. The compound according to claim 1, which is a compound represented by the following formula (1): [In formula (1), X represents m represented by formula (X1)] Ｙ +n Ｙ is a valent group, R ３ is a residue obtained by removing one hydroxy group and one allyl group from an allyl compound (D) containing a hydroxy group and an allyl group, or a single bond, and R ４ is a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from a (meth)acrylate compound (E) containing a hydroxy group and a (meth)acryloyloxy group, and R ５ is a hydroxyl atom or a methyl group, R ６ is an oxygen atom or a sulfur atom, m Ｙ is an integer from 1 to 4, and n Ｙ is an integer from 0 to 3, and m Ｙ +n Ｙ is an integer of 2 to 4. In formula (X1), R １ is a residue obtained by removing all mercapto groups from a thiol compound (B) containing 2 to 4 mercapto groups, and R ２ is a residue obtained by removing all iso(thio)cyanato groups from an iso(thio)cyanato compound (C) containing two iso(thio)cyanato groups, and n Ｘ is m in formula (1) Ｙ +n Ｙ and * indicates a bonding position. ６ In formula (1), R ２ If there are multiple R ２ In formula (1), R ３ If there are multiple R ３ In formula (1), R ４ If there are multiple R ４ In formula (1), R ５ If there are multiple R ５ may be the same or different.

7. The compound according to claim 6, wherein the thiol compound (B) includes a compound represented by any one of the following formulas (B1) to (B16): [In formula (B16), R Ｂ is a divalent organic group having 1 to 20 carbon atoms.

8. The compound according to claim 6, wherein the isocyanate compound (C) includes a compound represented by any one of the following formulas (C1) to (C8):

9. The compound according to claim 6, wherein the allyl compound (D) includes a compound represented by any one of the following formulas (D1) to (D4):

10. The compound according to claim 6, wherein the (meth)acrylate compound (E) includes a compound represented by the following formula (E1): [In formula (E1), R Ｅ１ is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R Ｅ２ is a hydrogen atom or a methyl group.

11. A monomer composition comprising the compound according to any one of claims 1 to 10.

12. The monomer composition of claim 11, used in the manufacture of dental products.

13. A curable composition comprising the monomer composition according to claim 11 and a polymerization initiator.

14. The hardenable composition of claim 13 for use in the manufacture of a dental product.

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

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