Monomer composition, curable composition, molded article, and method for producing monomer composition

Abstract

This monomer composition contains (A) a non-tin catalyst and (D) a (meth)acrylate monomer that is a reaction product of (B) an iso(thio)cyanate compound and (C) an alcohol compound. With respect to this monomer composition, the content of amide compounds which contain at least one of a carboxylic acid amide group and a sulfonamide group is less than 1 ppm by mass relative to the total mass of the monomer composition.

Description

[Technical Field]

[0001] The present disclosure relates to a monomer composition, a curable composition, a molded article, and a method for producing the monomer composition. [Background technology]

[0002] Urethane (meth)acrylate is known as a monomer contained in a curable composition. Urethane (meth)acrylate is a (meth)acrylate compound containing a urethane bond. Conventionally, urethane (meth)acrylates have been synthesized using Sn (tin)-based catalysts. For example, Patent Document 1 discloses a dental composite filler that is a mixture of a fine inert inorganic filler powder and a reaction product of an organic diisocyanate with an oxyalkyl acrylate or oxyalkyl methacrylate. In the examples of Patent Document 1, dibutyltin dilaurate is used as a catalyst to react oxypropyl methacrylate with 2,2,4-trimethylhexamethylene diisocyanate to form diurethane dimethacrylate.

[0003] Patent document 1: Japanese Patent Application Laid-Open No. 51-36960 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, from the viewpoint of reducing the amount of heavy metals used, there has been a demand for catalysts to replace Sn-based catalysts (for example, dibutyltin dilaurate (DBTDL)) as catalysts used in the formation of urethane (meth)acrylates. When a monomer composition containing a specific urethane (meth)acrylate monomer is used as a raw material for a dental material, it is desirable that the color of the monomer composition be suitable for the dental material. The specific urethane (meth)acrylate monomer is obtained by reacting an iso(thio)cyanate compound containing an iso(thio)cyanate group with a (meth)acrylate compound containing a hydroxyl group using a catalyst. Specifically, it is desirable that the color of the monomer composition is not yellowish.

[0005] An object of one aspect of the present disclosure is to provide a monomer composition, a curable composition, a molded body, and a method for producing the monomer composition, which have a color suitable for dental materials even when a catalyst alternative to a Sn-based catalyst is used. [Means for solving the problem]

[0006] The means for solving the above problems include the following embodiments. <1> A monomer composition comprising a non-tin catalyst (A) and a (meth)acrylate monomer (D) which is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (C), A monomer composition, wherein the content of an amide compound containing at least one of a carboxylic acid amide group and a sulfonamide group is less than 1 ppm by mass based on the total amount of the monomer composition. <2> The non-tin catalyst (A) contains a ligand, The ligand includes a group having at least one of a diketone structure and a double bond other than a carbonyl bond. <1> The monomer composition according to claim 1. <3> The non-tin catalyst (A) contains at least one of a compound represented by the following formula (X), a compound represented by the following formula (Y), and a compound represented by the following formula (Z): <1> or <2> The monomer composition according to claim 1.

[0007] [ka]

[0008] (In formula (X), RX1 and R X2 are each independently a monovalent hydrocarbon group. X is a metal atom other than tin. X is M X The valence of R exists multiple times. X1 and R X2 may be the same or different.)

[0009] [ka]

[0010] (In formula (Y), R Y1 and R Y2 are each independently a monovalent hydrocarbon group. Y is a metal atom other than tin. Y is M Y The valence of R exists multiple times. Y1 and R Y2 may be the same or different.)

[0011] [ka]

[0012] (In formula (Z), R Z1 is a halogen atom. Z is a metal atom other than tin. Z is M Z is the valence of m Z is an integer of 1 or 0.) <4> the non-tin catalyst (A) contains a metal atom other than tin, The metal atom other than tin is an atom of a metal element belonging to any one of the 4th to 6th periods and any one of the 4th to 14th groups (excluding tin atoms). <1> ~ <3> 1. The monomer composition according to any one of the preceding claims. <5> The non-tin catalyst (A) includes at least one selected from the group consisting of zinc-based catalysts, copper-based catalysts, indium-based catalysts, and platinum-based catalysts. <1> ~ <4> 1. The monomer composition according to any one of the preceding claims. <6> The isocyanate compound (B) contains an aromatic ring. <1> ~ <5> 1. The monomer composition according to any one of the preceding claims. <7> The iso(thio)cyanate compound (B) includes a reaction product (X) of an iso(thio)cyanate compound (b1) not containing a thiourethane bond or an iso(thio)cyanate compound (b2) not containing a thiourethane bond with a thiol compound (F) containing two or more mercapto groups. <1> ~ <6> 1. The monomer composition according to any one of the preceding claims. <8> The iso(thio)cyanate compound (b1) and the iso(thio)cyanate compound (b2) each contain at least one selected from the group consisting of m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. <7> The monomer composition according to claim 1. <9> The alcohol compound (C) includes at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, ethylene glycol, and glycerin. <1> ~ <8> 1. The monomer composition according to any one of the preceding claims. <10> The stabilizer (E) is at least one of a phosphite ester compound and a phenol compound. <1> ~ <9> 1. The monomer composition according to any one of the preceding claims. <11> The iso(thio)cyanate compound (B) is a reaction product of an iso(thio)cyanate compound (b2) not containing a thiourethane bond and a thiol compound (F) containing two or more mercapto groups. <1> ~ <10> 1. The monomer composition according to any one of the preceding claims. <12> The aforementioned <1> ~ <11> A curable composition comprising the monomer composition according to any one of the above items. <13> The composition further contains a polymerization initiator. <12> The curable composition according to claim 1. <14> The dental material composition, <12> or <13> The curable composition according to claim 1. <15> The aforementioned <12> ~ <14> A molded article which is a cured product of the curable composition according to any one of the above items. <16> A method for producing a monomer composition containing a non-tin catalyst (A) and a (meth)acrylate monomer (D) which is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (C), comprising the steps of: The method includes a step of mixing the non-tin catalyst (A), the iso(thio)cyanate compound (B), and the alcohol compound (C), A method for producing a monomer composition, wherein the content of an amide compound containing at least one of a carboxylic acid amide group and a sulfonamide group is less than 1 ppm by mass based on the total amount of the monomer composition. [Effects of the Invention]

[0013] According to one aspect of the present disclosure, there are provided a monomer composition, a curable composition, a molded body, and a method for producing the monomer composition, which have a color suitable for dental materials even when a catalyst instead of a Sn-based catalyst is used. DETAILED DESCRIPTION OF THE INVENTION

[0014] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present 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 the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In the numerical ranges described in this disclosure, the upper or lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, the term "light" is a concept that encompasses active energy rays such as ultraviolet light and visible light. In this disclosure, "(meth)acrylic monomer" means an acrylic monomer or a methacrylic monomer, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group, "(meth)acrylate" means an acrylate or a methacrylate, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylonitrile" means acrylonitrile or methacrylonitrile. In the present disclosure, "iso(thio)cyanate group" means an isocyanate group or an isothiocyanate group, and "iso(thio)cyanate compound" means an isocyanate compound or an isothiocyanate compound. In the present disclosure, the term "amide compound" refers to an amide compound containing at least one of a carboxylic acid amide group and a sulfonamide group. In the present disclosure, the phrase "the content of the amide compound is less than 1 ppm by mass relative to the total amount of the monomer composition" includes the case where the content of the amide compound is 0 parts by mass relative to the total amount of the monomer composition. In the present disclosure, a —NHC(═O)O— bond and a —NHC(═S)O— bond are collectively referred to as a “urethane bond,” and a compound containing at least one of a —NHC(═O)O— bond and a —NHC(═S)O— bond and a (meth)acryloyl group is also referred to as a urethane(meth)acrylate. The preferred configurations described in the monomer composition, curable composition, molded article, and method for producing a monomer composition of the present disclosure may be combined as appropriate. For example, the configuration disclosed in the monomer composition may be combined as appropriate with the method for producing a monomer composition, etc.

[0015] [Monomer composition] The monomer composition of the present disclosure is a monomer composition containing a non-tin catalyst (A) and a (meth)acrylate monomer (D) which is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (C), and the content of an amide compound containing at least one of a carboxylic acid amide group (-C(=O)NH2) and a sulfonamide group (-S(=O)2NH2) is less than 1 mass ppm relative to the total amount of the monomer composition. The monomer composition of the present disclosure has the above-described structure, and therefore has a hue suitable for dental materials even when a catalyst other than a Sn-based catalyst is used. Specifically, the hue of the monomer composition of the present disclosure is not yellowish. Therefore, by using the monomer composition of the present disclosure, a cured product having a hue suitable for dental materials can be produced.

[0016] As mentioned above, from the viewpoint of reducing the amount of heavy metals used, etc., there is a demand for catalysts to replace Sn-based catalysts as catalysts used in the formation of urethane (meth)acrylates. Furthermore, as a raw material for dental materials, it is desirable that the color of the monomer composition is suitable for dental materials (for example, not yellowish). On the other hand, when a commercially available iso(thio)cyanate compound is used as a raw material in the presence of a non-tin catalyst (e.g., a zinc catalyst), the resulting monomer composition may have a yellowish hue. Typically, commercially available iso(thio)cyanate compounds contain a stabilizer. As a result of extensive research, the present inventors have discovered that the main cause of the yellowish hue of a monomer composition when a non-tin catalyst (e.g., a zinc catalyst) is used is an amide compound, and have completed the present disclosure. Amide compounds are contained as stabilizers in commercially available isocyanate compounds.

[0017] As described above, the amide compound may be contained in a commercially available product. For example, by using a purified product obtained by purifying a commercially available product by a known method as a raw material for the monomer composition, the content of the amide compound can be within the above range.

[0018] Components that may be contained in the monomer composition of the present disclosure will be described below.

[0019] <Non-tin catalyst (A)> The monomer composition of the present disclosure contains a non-tin-based catalyst (A). The non-tin catalyst (A) is a catalyst containing a metal atom other than a tin atom, such as a zinc atom, a titanium atom, a zirconium atom, a bismuth atom, an iron atom, a copper atom, or a cobalt atom. The non-tin catalyst (A) is a catalyst used in the production of the (meth)acrylate monomer (D) (that is, in the reaction of the iso(thio)cyanate compound (B) with the alcohol compound (C)). The non-tin catalyst (A) contained in the monomer composition of the present disclosure may be of one type only, or may be of two or more types.

[0020] When the non-tin catalyst (A) is a specific compound containing a ligand, the use of the monomer composition as a dental material is less likely to cause color problems (e.g., less yellowing). The ligand of the specific compound is only one or more ligands selected from the group consisting of alkyl groups, carboxyl groups, alkoxy groups, and halogeno groups. On the other hand, if the non-tin catalyst (A) contains a ligand other than these, the use of the monomer composition as a dental material may cause problems with color (for example, yellowing). However, the monomer composition of the present disclosure contains an amide compound in an amount of less than 1 ppm by mass, and therefore, even if the non-tin catalyst (A) is a compound other than the above-mentioned specific compounds, the color is less likely to deteriorate, and a monomer composition having a color more suitable for dental materials can be obtained. From the viewpoint of being able to suppress a decrease in hue in this way, when the non-tin-based catalyst (A) in the present disclosure contains a ligand, it is preferably the first compound, more preferably the second compound, and even more preferably the third compound. The first compound is a compound other than a compound in which the ligand is only one or more ligands selected from the group consisting of an alkyl group and a carboxyl group. The second compound is a compound other than a compound whose only ligand is one or more selected from the group consisting of an alkyl group, a carboxyl group, and an alkoxy group. The third compound is a compound other than a compound whose only ligand is one or more selected from the group consisting of an alkyl group, a carboxyl group, an alkoxy group, and a halogeno group. Examples of the alkyl group that is a ligand include alkyl groups having 1 to 20 carbon atoms (which may be linear or branched). Examples of the carboxyl group that is a ligand include a carboxyl group represented by the general formula RC(=O)-O-, where R is an alkyl group (which may be linear or branched) having 1 to 20 carbon atoms. Examples of the alkoxy group that is a ligand include an alkoxy group represented by the general formula RO-, in which R is an alkyl group (which may be linear or branched) having 1 to 20 carbon atoms. Examples of the halogeno group that is a ligand include a fluoro group (F-), a chloro group (Cl-), a bromo group (Br-), and an iodo group (I-).

[0021] If the absorbance of the non-tin catalyst (A) in the wavelength range of 250 nm to 800 nm is 0.05 or more, when the monomer composition is used as a dental material, problems with color may arise (for example, yellowish tinge may occur). However, since the monomer composition of the present disclosure has an amide compound content of less than 1 ppm by mass, even if the absorbance in the wavelength range of 250 nm to 800 nm is 0.05 or more, the hue is less likely to decrease, and a monomer composition having a hue more suitable for dental materials can be obtained. From the viewpoint of being able to suppress a decrease in hue in this way, the monomer composition of the present disclosure is suitable when the non-tin catalyst (A) has an absorbance of 0.05 or more in a wavelength range of 250 nm to 800 nm. The absorbance of the non-tin-based catalyst (A) is measured by dissolving the non-tin-based catalyst (A) in tetrahydrofuran (containing no stabilizer) to prepare a 0.01 mmol / L solution, placing the resulting solution in a quartz cell with a cell length of 1 cm, and using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, "V-650").

[0022] The non-tin catalyst (A) contains a ligand, and the ligand may contain a group having at least one of a diketone structure and a double bond other than a carbonyl bond. Double bonds other than carbonyl bonds tend to absorb light of a specific wavelength (e.g., visible light) and develop color, or tend to produce hues through addition reactions with functional groups different from ketones during the process of producing the monomer composition. Diketone structures tend to produce hues through addition reactions with functional groups different from ketones during the process of producing the monomer composition. The resulting addition reactive groups tend to absorb light of a specific wavelength (e.g., visible light) and develop color. The monomer composition of the present disclosure has an amide compound content of less than 1 ppm by mass, and therefore, even when the ligand of the non-tin catalyst (A) contains a group having at least one of a diketone structure and a double bond other than a carbonyl bond, the color of the monomer composition of the present disclosure is suitable for dental materials.

[0023] Examples of groups having a double bond other than a carbonyl bond include aromatic groups, thiocarbonyl groups, heteroaromatic groups, and alkenyl groups. Aromatic groups, thiocarbonyl groups, and heteroaromatic groups tend to exhibit a hue themselves, while alkenyl groups tend to exhibit a hue through an addition reaction. Examples of aromatic groups include phenyl groups, naphthyl groups, and biphenyl groups. Examples of groups having a thiocarbonyl group include thiocarbamate groups, thiobenzamide groups, thioacetamide groups, and thiourea groups. Examples of heteroaromatic groups include 3- to 6-membered rings having a nitrogen atom, sulfur atom, or oxygen atom, more specifically, furan groups, thiophene groups, oxazole groups, thiazole groups, pyridine groups, pyran groups, and thiopyran groups. Examples of alkenyl groups include allyl groups, vinyl groups, vinylidene groups, and vinylene groups.

[0024] The group having a diketone structure may be a ligand having two ketone groups, and is preferably a ligand having a β-diketone. Examples of the ligand having a β-diketone include acetylacetonate, 3-methylacetylacetonate, 3-ethylacetylacetonate, 3-phenylacetylacetonate, trifluoroacetylacetonate, hexafluoroacetylacetonate, and diisobutylmethane.

[0025] The non-tin catalyst (A) preferably contains at least one of a compound represented by the following formula (X) (hereinafter referred to as "compound (X)"), a compound represented by the following formula (Y) (hereinafter referred to as "compound (Y)"), and a compound represented by the following formula (Z) (hereinafter referred to as "compound (Z)"), and more preferably contains compound (X) or compound (Y). When the non-tin catalyst (A) contains these compounds, a hue is likely to occur, but the monomer composition of the present disclosure can suppress this hue.

[0026] The compound (X) is represented by the following formula (X).

[0027] [ka]

[0028] In formula (X), R X1 and R X2 are each independently a monovalent hydrocarbon group. X is a metal atom other than tin. X is M X The valence of R exists multiple times. X1 and R X2 may be the same or different.

[0029] R X1 and R X2 Examples of the monovalent hydrocarbon group in include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylaryl group, an alkenylaryl group, an alkynylaryl group, an arylalkyl group, an arylalkenyl group, and an arylalkynyl group. R X1 and R X2 are each independently preferably an alkyl group or an aryl group. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms, and more specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. The aryl group includes a phenyl group. M X is a metal atom other than tin, and is only required to have catalytic activity. It is preferably a specific metal atom, and more preferably zinc, copper, indium or platinum. In the present disclosure, the term "specific metal atom" refers to a metal element belonging to any one of Periods 4 to 6 and any one of Groups 4 to 14. Specifically, the specific metal atom refers to titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, and lead.

[0030] The non-tin catalyst (A) containing the compound (A) contains a compound represented by the following formula (1). Specific examples of the non-tin catalyst (A) containing the compound (A) include zinc dibutyldithiocarbamate.

[0031] [ka]

[0032] In formula (Y), R Y1 and R Y2 are each independently a monovalent hydrocarbon group. Y is a metal atom other than tin. Y is M Y The valence of R exists multiple times. Y1 and R Y2 may be the same or different.

[0033] R Y1 and R Y2 Examples of the "monovalent hydrocarbon group" in the above formula include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylaryl group, an alkenylaryl group, an alkynylaryl group, an arylalkyl group, an arylalkenyl group, and an arylalkynyl group. R Y1 and R Y2 are each independently preferably an alkyl group or an aryl group. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms, and more specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. The aryl group includes a phenyl group. M Y is a metal atom other than tin, and is only required to have catalytic activity. It is preferably a specific metal atom, and more preferably zinc, copper, indium or platinum.

[0034] Specific examples of the non-tin catalyst (A) containing the compound (B) include indium acetylacetonate and platinum acetylacetonate.

[0035] [ka]

[0036] In formula (Z), R Z1 is a halogen atom. Z is a metal atom other than tin. Z is M Z is the valence of m Z is an integer of 1 or 0.

[0037] R Z1 The halogen atom in is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, still more preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom. M Z is a metal atom other than tin, and is only required to have catalytic activity. It is preferably a specific metal atom, and more preferably zinc, copper, indium or platinum.

[0038] Specific examples of the non-tin catalyst (A) containing the compound (C) include tris(triphenylphosphine)(trifluoromethyl)copper.

[0039] The non-tin catalyst (A) preferably contains a metal atom other than tin. The metal atom other than tin is a specific metal atom, i.e., an atom of a metal element (excluding tin atoms) belonging to any one of Periods 4 to 6 and Groups 4 to 14. This allows the non-tin catalyst (A) to exhibit catalytic activity in the synthesis reaction of the (meth)acrylate monomer (D) of the present disclosure, even without a tin atom.

[0040] As the non-tin-based catalyst (A), a catalyst containing the above-mentioned specific metal atoms can be used, and examples thereof include zinc-based catalysts, titanium-based catalysts, zirconium-based catalysts, bismuth-based catalysts, iron-based catalysts, copper-based catalysts, cobalt-based catalysts, indium-based catalysts, and platinum-based catalysts. For example, zinc-based catalysts contain zinc atoms; titanium-based catalysts contain titanium atoms; zirconium-based catalysts contain zirconium atoms; bismuth-based catalysts contain bismuth atoms; iron-based catalysts contain iron atoms; copper-based catalysts contain copper atoms; cobalt-based catalysts contain cobalt atoms; indium-based catalysts contain indium atoms; and platinum-based catalysts contain platinum atoms.

[0041] The non-tin catalyst (A) preferably contains at least one selected from the group consisting of zinc-based catalysts, copper-based catalysts, indium-based catalysts and platinum-based catalysts.

[0042] As the zinc-based catalyst, known zinc-based catalysts can be used. The zinc-based catalyst may be any catalyst containing at least one zinc atom, and is preferably, for example, at least one of a sulfur-containing compound containing a sulfur atom and an oxygen-containing compound containing an oxygen atom. The sulfur-containing compound containing a sulfur atom and the oxygen-containing compound containing an oxygen atom are preferably at least one of a dithiocarbamate catalyst containing a zinc atom and a zinc compound containing a zinc atom and a ring structure.

[0043] The dithiocarbamate catalyst containing a zinc atom is preferably a zinc dithiocarbamate compound.The zinc compound containing a zinc atom and a ring structure is preferably a zinc compound containing a zinc atom and an aromatic ring or a heterocyclic ring, and more preferably a zinc compound containing a bisthiozinc skeleton (-S-Zn-S-) or a bisoxyzinc skeleton (-O-Zn-O-) and an aromatic ring or a heterocyclic ring.

[0044] The non-tin catalyst (A) is preferably at least one of a compound represented by the following formula (1) and a compound represented by the following formula (2). The compound represented by the following formula (2) may be a zinc complex. In particular, it is preferable to contain a compound represented by the following formula (1).

[0045] [ka]

[0046] [ka]

[0047] In equation (1), two R 1 and two R 2 are each independently a monovalent hydrocarbon group.

[0048] R 1 and R 2 Examples of the monovalent hydrocarbon group in include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylaryl group, an alkenylaryl group, an alkynylaryl group, an arylalkyl group, an arylalkenyl group, and an arylalkynyl group.

[0049] R 1 and R 2 are each independently preferably an alkyl group or an aryl group. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms, and more specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. The aryl group includes a phenyl group.

[0050] Specific examples of the compound represented by the above formula (1) include zinc dibutyldithiocarbamate.

[0051] In formula (2), X 1 and X 2 are each independently an oxygen atom or a sulfur atom. 3 and R 4 are each independently a monovalent organic group containing an aromatic ring or a heterocyclic ring, or R 3 and R 4 are organic groups that bond together to form a ring structure.

[0052] R 3 and R 4In the above, examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and among these, a benzene ring is preferred. R 3 and R 4 In the above, examples of the heterocyclic ring include ring structures containing a nitrogen atom, a sulfur atom, an oxygen atom, etc., and among these, heterocyclic rings having aromaticity are preferred. Specific examples of the heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, an isoindole ring, a thiophene ring, a benzothiophene ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, an indazole ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, a pyridine ring, a quinoline ring, a pyrazine ring, a quinoxaline ring, a pyrimidine ring, a pyridazine ring, and a triazine ring. Of these, a pyridine ring and a benzothiazole ring are preferred. R 3 and R 4 may each contain one or more aromatic rings and one or more heterocyclic rings, or may contain multiple aromatic rings or multiple heterocyclic rings. For example, R 3 and R 4 Preferably, each of the groups contains a benzene ring and a benzothiazole ring.

[0053] R 3 and R 4 Examples of the ring structure formed by bonding R to each other include the aromatic rings and heterocyclic rings described above, and among these, a benzene ring is preferred. 3 and R 4 When they are bonded to each other, the ring structure is 1 and X 2 Preferably, the ring structure comprises a ring containing a zinc atom, and an aromatic ring or a heterocyclic ring. More preferably, the ring structure is a fused ring that shares two carbon atoms. R 3 and R 4 In the formula (I), the monovalent organic group containing an aromatic ring or a heterocyclic ring and the organic group forming a ring structure may each independently contain a substituent, such as an alkyl group having 1 to 6 carbon atoms, or an aryl group such as a phenyl group.

[0054] Specific examples of the compound represented by the above formula (2) include compounds having the following structures.

[0055] [ka]

[0056] As the copper-based catalyst, known copper-based catalysts can be used. The copper-based catalyst may be any catalyst containing at least one copper atom, and may contain, for example, a copper atom and a ligand. Examples of the ligand of the copper-based catalyst include acetylacetonate, tris(triphenylphosphine)(trifluoromethyl), tetrakis(triphenylphosphine), etc. A specific example of the copper-based catalyst is tris(triphenylphosphine)(trifluoromethyl)copper.

[0057] As the indium-based catalyst, known indium-based catalysts can be used. The indium-based catalyst may be any catalyst containing at least one indium atom, and may contain, for example, an indium atom and a ligand. Examples of the ligand for the indium-based catalyst include the same ligands as those exemplified as the ligand for the copper-based catalyst. Specific examples of indium catalysts include indium acetylacetonate.

[0058] As the platinum catalyst, known platinum catalysts can be used. The platinum-based catalyst may be any catalyst containing at least one platinum atom, and may contain, for example, a platinum atom and a ligand. Examples of the ligand for the platinum-based catalyst include the same ligands as those exemplified as the ligand for the copper-based catalyst. Specific examples of platinum catalysts include platinum acetylacetonate.

[0059] The content of the non-tin catalyst (A) in the monomer composition of the present disclosure is preferably 0.01 mass% to 1 mass%, more preferably 0.03 mass% to 0.7 mass%, and even more preferably 0.05 mass% to 0.5 mass%, relative to the total amount of the monomer composition.

[0060] In the monomer composition of the present disclosure, the content of the zinc-based catalyst may be 0.5% by mass or less, 0.3% by mass or less, or 0.1% by mass or less, relative to the total amount of the monomer composition.

[0061] The monomer composition of the present disclosure may or may not contain a non-tin-based catalyst (A) other than a zinc-based catalyst (hereinafter also referred to as "other catalyst"). Examples of other catalysts include catalysts containing metal atoms other than tin atoms and zinc atoms.

[0062] The content of the other catalyst in the monomer composition of the present disclosure may be 0.5% by mass or less, 0.3% by mass or less, or 0.1% by mass or less, based on the total amount of the monomer composition. The lower limit of the content of the other catalyst in the monomer composition of the present disclosure is not particularly limited, and may be 0% by mass from the viewpoint of reducing the use of heavy metals such as tin.

[0063] <(Meth)acrylate Monomer (D)> The monomer composition of the present disclosure contains a (meth)acrylate monomer (D). The (meth)acrylate monomer (D) contained in the monomer composition of the present disclosure may be of one type only, or may be of two or more types.

[0064] The monomer composition of the present disclosure can be used, for example, as a component in the curable composition described below (specifically, as a source of monomer for the curable composition described below). The monomer composition of the present disclosure itself can be used as the curable composition.

[0065] The (meth)acrylate monomer (D) is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (B). The iso(thio)cyanate compound (B) contains an iso(thio)cyanate group. The alcohol compound (B) contains a hydroxyl group.

[0066] The (meth)acrylate monomer (D) preferably contains a urethane bond (i.e., at least one of an -NHC(=O)O- bond and an -NHC(=S)O- bond; the same applies hereinafter) formed by the reaction of an iso(thio)cyanate group in the iso(thio)cyanate compound (B) with a hydroxy group in the alcohol compound (C), and also contains a (meth)acryloyl group. The (meth)acryloyl group of the (meth)acrylate monomer (D) is preferably derived from at least one of the iso(thio)cyanate compound (B) and the alcohol compound (C). That is, the (meth)acrylate monomer (D) is preferably a urethane (meth)acrylate.

[0067] The (meth)acrylate monomer (D) preferably contains a thiourethane bond (i.e., at least one of an -NHC(=O)S- bond and an -NHC(=S)S- bond; the same applies hereinafter) formed by the reaction of an iso(thio)cyanate group in the iso(thio)cyanate compound (b2) described below with a mercapto group in the thiol compound (F), and also contains a (meth)acryloyl group. The (meth)acryloyl group of the (meth)acrylate monomer (D) is preferably derived from at least one of the iso(thio)cyanate compound (B) and the alcohol compound (C). That is, the (meth)acrylate monomer (D) is preferably a thiourethane (meth)acrylate. The thiourethane (meth)acrylate preferably contains a urethane bond (i.e., a —NHC(═O)O— bond and a —NHC(═S)O— bond) formed by the reaction of an iso(thio)cyanate group in the iso(thio)cyanate compound (B) with a hydroxy group in the alcohol compound (C).

[0068] In the monomer composition of the present disclosure, the content of the (meth)acrylate monomer (D) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total amount of the monomer composition.

[0069] In the monomer composition of the present disclosure, the total content of the (meth)acrylate monomer (D), the iso(thio)cyanate compound (B), and the alcohol compound (C) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total amount of the monomer composition.

[0070] The iso(thio)cyanate compound (B) and the (meth)acrylate compound (C) contained in the raw material composition for the (meth)acrylate monomer (D) will be described below. Furthermore, the thiol compound (F) that can be contained in the raw material composition for the (meth)acrylate monomer (D) will be described.

[0071] (Iso(thio)cyanate compound (B)) The raw material composition of the (meth)acrylate monomer (D) contains an iso(thio)cyanate compound (B). The iso(thio)cyanate compound (B) contains an iso(thio)cyanate group. The iso(thio)cyanate compound (B) containing an iso(thio)cyanate group contained in the monomer composition of the present disclosure may be of one type only, or may be of two or more types. The number of iso(thio)cyanate groups in the iso(thio)cyanate compound (B) is preferably 2-4. It is preferred that at least one of the iso(thio)cyanate compound (B) and the alcohol compound (C) contains a (meth)acryloyl group. When the alcohol compound (C) contains a (meth)acryloyl group, the iso(thio)cyanate compound (B) may or may not contain a (meth)acryloyl group. When the alcohol compound (C) does not contain a (meth)acryloyl group, the iso(thio)cyanate compound (B) contains a (meth)acryloyl group. The iso(thio)cyanate compound (B) preferably contains an aromatic ring.

[0072] In the present disclosure, examples of the iso(thio)cyanate compound (B) include the iso(thio)cyanate compound (b1) and the reaction product (X). The iso(thio)cyanate compound (b1) is an iso(thio)cyanate compound itself that does not contain a thiourethane bond. The reaction product (X) is a reaction product of an iso(thio)cyanate compound (b2) containing no thiourethane bond and a thiol compound (F) containing two or more mercapto groups. Details of the thiol compound (F) will be described later. The iso(thio)cyanate compound (B) preferably contains the iso(thio)cyanate compound (b1) or the reaction product (X). In particular, the iso(thio)cyanate compound (B) is preferably the reaction product (X). In other words, the (meth)acrylate monomer (D) is preferably the reaction product (Y) of the reaction product (X) and the alcohol compound (B). In this case, the (meth)acrylate monomer (D) contains a thiourethane bond formed by the reaction of the iso(thio)cyanate group in the reaction product (X) (i.e., the iso(thio)cyanate group derived from the iso(thio)cyanate compound (b2)) with the mercapto group in the thiol compound (F), and also contains a (meth)acryloyl group.

[0073] Hereinafter, the iso(thio)cyanate compound (b1) and the iso(thio)cyanate compound (b2) that is a raw material for the reaction product (X) will be collectively referred to as "iso(thio)cyanate compound (b)."

[0074] The isocyanate compound (b) is preferably an isocyanate compound containing two or more (more preferably two or three, and even more preferably two) isocyanate groups, and more preferably, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, isophorone diisocyanate, bis(isocyanate), and at least one selected from the group consisting of 2,5-bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, and 2-isocyanatoethyl (meth)acrylate.

[0075] The iso(thio)cyanate compound (b) (particularly, the iso(thio)cyanate compound (b1) and the iso(thio)cyanate compound (b2)) more preferably includes at least one selected from the group consisting of m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0076] Among the iso(thio)cyanate compounds (b), examples of the thioisocyanate compound include aliphatic polyisothiocyanate compounds, alicyclic polyisothiocyanate compounds, aromatic polyisothiocyanate compounds, and sulfur-containing heterocyclic polyisothiocyanate compounds. Examples of the aliphatic polyisothiocyanate compound include hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate, m-xylylene diisothiocyanate, bis(isothiocyanate methyl) sulfide, bis(isothiocyanate ethyl) sulfide, and bis(isothiocyanate ethyl) disulfide. Examples of alicyclic polyisothiocyanate compounds include isophorone diisothiocyanate, bis(isothiocyanatemethyl)cyclohexane, dicyclohexylmethane diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2,5-bis(isothiocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isothiocyanatemethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isothiocyanatemethyl)tricyclodecane, 3,9-bis(isothiocyanatemethyl)tricyclodecane, 4,8-bis(isothiocyanatemethyl)tricyclodecane, and 4,9-bis(isothiocyanatemethyl)tricyclodecane. Examples of aromatic polyisothiocyanate compounds include tolylene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, and diphenyl disulfide-4,4-diisothiocyanate. Examples of sulfur-containing heterocyclic polyisothiocyanate compounds include 2,5-diisothiocyanate thiophene, 2,5-bis(isothiocyanate methyl) thiophene, 2,5-isothiocyanate tetrahydrothiophene, 2,5-bis(isothiocyanate methyl) tetrahydrothiophene, 3,4-bis(isothiocyanate methyl) tetrahydrothiophene, 2,5-diisothiocyanate 1,4-dithiane, 2,5-bis(isothiocyanate methyl)-1,4-dithiane, 4,5-diisothiocyanate 1,3-dithiolane, and 4,5-bis(isothiocyanate methyl)-1,3-dithiolane.

[0077] In the present disclosure, when a commercially available product is used as a raw material for the iso(thio)cyanate compound (B), it is preferable to use an iso(thio)cyanate compound (B) obtained by purifying the commercially available product by a known method. The commercially available product may contain an amide compound as a stabilizer. If a commercially available product containing an amide compound is used as the iso(thio)cyanate compound (B) without purification, the color of the monomer composition may become yellowish due to the amide compound contained in the commercially available product.

[0078] (Alcohol compound (C)) The raw material composition of the (meth)acrylate monomer (D) contains an alcohol compound (C). The alcohol compound (C) contains a hydroxy group. The alcohol compound (C) contained in the raw material composition of the (meth)acrylate monomer (D) may be one type only, or two or more types. It is preferred that at least one of the iso(thio)cyanate compound (B) and the alcohol compound (C) contains a (meth)acryloyl group. When the iso(thio)cyanate compound (B) contains a (meth)acryloyl group, the alcohol compound (C) may or may not contain a (meth)acryloyl group. When the iso(thio)cyanate compound (B) does not contain a (meth)acryloyl group, the alcohol compound (C) contains a (meth)acryloyl group.

[0079] The alcohol compound (C) is preferably at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, ethylene glycol, and glycerin.

[0080] In the monomer composition of the present disclosure, the molar ratio of hydroxy groups in the alcohol compound (C) to iso(thio)cyanate groups in the iso(thio)cyanate compound (B) (i.e., molar ratio [hydroxy groups / iso(thio)cyanate groups]) is preferably 0.3 to 2, more preferably 0.5 to 1.5, even more preferably 0.8 to 1.2, and still more preferably 0.9 to 1.1.

[0081] In the monomer composition of the present disclosure, the total content of the iso(thio)cyanate compound (B) and the alcohol compound (C) is preferably 90 mass% or more, and more preferably 95 mass% or more, based on the total amount of the monomer composition. The upper limit of the total content of the iso(thio)cyanate compound (B) and the alcohol compound (C) is appropriately determined depending on the content of the non-tin catalyst (A). Examples of the upper limit of the total content of the iso(thio)cyanate compound (B) and the alcohol compound (C) include 99.9 mass%, 99.7 mass%, and 99.5 mass%.

[0082] (Thiol Compound (F)) The raw material composition of the (meth)acrylate monomer (D) may contain a thiol compound (F), whereby the (meth)acrylate monomer (D) is obtained, for example, as a reaction product (Y) between a reaction product (X) obtained by reacting an iso(thio)cyanate compound (b2) with the thiol compound (F) and an alcohol compound (C). The thiol compound (F) contained in the raw material composition of the (meth)acrylate monomer (D) may be of one type only, or may be of two or more types. The number of mercapto groups in the thiol compound (F) is preferably 2 or more, more preferably 3 or more, still more preferably 3 to 6, particularly preferably 3 to 5, and even more preferably 3 or 4.

[0083] For the thiol compound (F), for example, the description in paragraphs 0045 to 0087 of WO 2019 / 107323 can be appropriately referred to.

[0084] The thiol compound (F) is preferably at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-dimercaptomethyl-1,4-dithiane, bis(mercaptoethyl) sulfide, and diethylene glycol bis(mercaptopropionate). The thiol compound (F) is more preferably at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), and pentaerythritol tetrakis(3-mercaptopropionate).

[0085] In the monomer composition of the present disclosure, the molar ratio of the hydroxy group in the alcohol compound (C) and the mercapto group in the thiol compound (F) to the iso(thio)cyanate group in the iso(thio)cyanate compound (b2), which is a raw material for the reaction product (X) (i.e., the molar ratio [(hydroxy group + mercapto group) / iso(thio)cyanate group]) is preferably 0.3 to 2, more preferably 0.5 to 1.5, even more preferably 0.8 to 1.2, and still more preferably 0.9 to 1.1.

[0086] In the monomer composition of the present disclosure, the total content of the iso(thio)cyanate compound (b2), the alcohol compound (C), and the thiol compound (F), which are raw materials for the reaction product (X), is preferably 90 mass% or more, and more preferably 95 mass% or more, based on the total amount of the monomer composition. The upper limit of the total content of the iso(thio)cyanate compound (b2), the alcohol compound (C), and the thiol compound (F) is appropriately determined depending on the content of the non-tin catalyst (A). Examples of the upper limit of the total content of the iso(thio)cyanate compound (b2), the alcohol compound (C), and the thiol compound (F), which are raw materials for the reaction product (X), include 99.9 mass%, 99.7 mass%, and 99.5 mass%.

[0087] (Stabilizer (E)) The raw material composition of the (meth)acrylate monomer (D) may contain a stabilizer (E). The stabilizer (E) contained in the raw material composition of the (meth)acrylate monomer (D) may be one type only, or two or more types.

[0088] The stabilizer (E) is at least one of a phosphite ester compound and a phenol compound, i.e., the stabilizer (E) may be a phosphite ester compound, a phenol compound, or a combination of a phosphite ester compound and a phenol compound.

[0089] Examples of phosphite compounds include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono(tridecyl) phosphite, and tris(2,4-di-tert-butylphenyl) phosphite.

[0090] Examples of the phenolic compounds include phenol, meta-cresol, 2,5-ditertiaryamylhydroquinone, and 2,5-ditertiarybutylhydroquinone.

[0091] The content of the stabilizer (E) is preferably 10 ppm by mass to 10,000 ppm by mass, more preferably 50 ppm by mass to 5,000 ppm by mass, still more preferably 100 ppm by mass to 2,500 ppm by mass, and more preferably 200 ppm by mass to 1,000 ppm by mass, relative to the total amount of the monomer composition.

[0092] The monomer composition of the present disclosure may contain, in addition to the (meth)acrylate monomer (D) (i.e., the reaction product), at least one of an iso(thio)cyanate compound (B) and an alcohol compound (C) as an unreacted raw material.

[0093] <Polymerization inhibitor (G)> The monomer composition of the present disclosure may contain a polymerization inhibitor (G). When the monomer composition of the present disclosure contains a polymerization inhibitor (G), the polymerization inhibitor (G) contained may be of only one type, or may be of two or more types. The polymerization inhibitor (G) is not particularly limited, and examples thereof include dibutylhydroxytoluene (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), and phenothiazine (PTZ).

[0094] The content of the polymerization inhibitor (G) is preferably 0.001% by mass to 0.5% by mass, more preferably 0.002% by mass to 0.3% by mass, still more preferably 0.005% by mass to 0.3% by mass, and more preferably 0.01% by mass to 0.2% by mass, relative to the total amount of the monomer composition.

[0095] <Other Monomers> The monomer composition of the present disclosure may contain at least one other monomer in addition to the (meth)acrylate monomer (D) and its raw materials, the iso(thio)cyanate compound (B) and the alcohol compound (C). Examples of other monomers include (meth)acrylate monomers (D), (meth)acrylates other than the iso(thio)cyanate compounds (B) and the alcohol compounds (C) (hereinafter also referred to as "(meth)acrylate compounds (H)").

[0096] Examples of the (meth)acrylate compound (H) 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, and triethylene glycol di(meth)acrylate. acrylate, tetraethylene glycol di(meth)acrylate, 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, and the like.

[0097] When the monomer composition of the present disclosure contains other monomers (for example, a (meth)acrylate compound (H)), the content of the other monomers is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 50% by mass, even more preferably 10% by mass to 40% by mass, and still more preferably 20% by mass to 40% by mass, relative to the total content of the iso(thio)cyanate compound (B), the alcohol compound (C), the (meth)acrylate monomer (D) and other monomers (excluding compounds not containing a (meth)acryloyl group).

[0098] <Other ingredients> The monomer composition of the present disclosure may contain other components in addition to the components described above. Other components that may be contained in the monomer composition of the present disclosure include the components in the curable composition described below.

[0099] [Method for producing monomer composition] The method for producing a monomer composition of the present disclosure is a method for producing a monomer composition containing a non-tin catalyst (A) and a (meth)acrylate monomer (D) that is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (C), and includes a step of mixing the non-tin catalyst (A), the iso(thio)cyanate compound (B), and the alcohol compound (C) (hereinafter also referred to as the "mixing step"), in which the content of the amide compound containing at least one of a carboxylic acid amide group and a sulfonamide group is less than 1 ppm by mass with respect to the total amount of the monomer composition. The method for producing the monomer composition of the present disclosure may include other steps as necessary.

[0100] In the mixing step, the non-tin catalyst (A), the iso(thio)cyanate compound (B), and the alcohol compound (C) are mixed together to cause a reaction between the iso(thio)cyanate compound (B) and the alcohol compound (C), resulting in the production of a reaction product, a (meth)acrylate monomer (D). This makes it possible to produce the (meth)acrylate monomer (D) using a catalyst that replaces the Sn-based catalyst, and to produce a cured product with a color suitable for dental materials.

[0101] In the mixing step, the non-tin catalyst (A), the iso(thio)cyanate compound (b2) not containing a thiourethane bond, the alcohol compound (C), and the thiol compound (F) containing two or more mercapto groups may be mixed. In the mixing step, the non-tin catalyst (A), the iso(thio)cyanate compound (b2), the alcohol compound (C), and the thiol compound (F) are mixed together to cause a reaction between the iso(thio)cyanate compound (b2), the alcohol compound (C), and the thiol compound (F), resulting in the production of a (meth)acrylate monomer (D) as a reaction product. In the mixing step, the non-tin catalyst (A), the iso(thio)cyanate compound (b2) containing no thiourethane bond, and the thiol compound (F) containing two or more mercapto groups may be mixed, and then the alcohol compound (C) may be added and mixed. In other words, in the mixing step, the iso(thio)cyanate compound (b2) and the thiol compound (F) may be reacted by mixing to produce the reaction product (X), and then the reaction product (X) may be reacted with the alcohol compound (C) to produce the (meth)acrylate monomer (D), which is the reaction product (Y). This makes it possible to produce the (meth)acrylate monomer (D) using a catalyst that replaces the Sn-based catalyst, and to produce a cured product having a color suitable for dental materials.

[0102] In the mixing step, there are no particular limitations on the manner in which the components are mixed. A preferred embodiment for mixing the components is to first prepare a composition by mixing the non-tin catalyst (A) with either the iso(thio)cyanate compound (B) or the alcohol compound (C), and then add the other of the iso(thio)cyanate compound (B) and the alcohol compound (C) to the resulting composition and mix them in. At this time, the other of the iso(thio)cyanate compound (B) and the alcohol compound (C) may be gradually mixed in by dropwise addition, for example.

[0103] A more preferred embodiment of mixing the components is one in which one of the iso(thio)cyanate compound (B) and the alcohol compound (C) contains a (meth)acryloyl group and the other does not, and the components are mixed as follows: Specifically, a non-tin catalyst (A) is mixed with one of the iso(thio)cyanate compound (B) and the alcohol compound (C), which does not contain a (meth)acryloyl group, to prepare a composition, and then the other of the iso(thio)cyanate compound (B) and the alcohol compound (C), which does not contain a (meth)acryloyl group, is added to the resulting composition and mixed. This tends to suppress the polymerization reaction of the (meth)acryloyl group while allowing the reaction between the iso(thio)cyanate compound (B) and the alcohol compound (C) to proceed favorably.

[0104] The reaction temperature in the mixing step is preferably 40°C to 90°C, more preferably 50°C to 90°C, and even more preferably 60°C to 90°C.

[0105] The reaction time of the above reaction in the mixing step is preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 3 hours or more, from the viewpoint of further progressing the reaction between the iso(thio)cyanate compound (B) and the alcohol compound (C). The reaction time is preferably 30 hours or less, more preferably 25 hours or less, and even more preferably 20 hours or less, from the viewpoint of further suppressing decomposition and polymerization of the (meth)acrylate monomer (D) and side reactions between the iso(thio)cyanate compounds (B).

[0106] The preferred range of the amount of the non-tin catalyst (A) used in the mixing step is the same as the preferred range of the content of the non-tin catalyst (A) in the monomer composition of the present disclosure.

[0107] The preferred ranges of the molar ratio [hydroxy group / iso(thio)cyanate group] and the total amount of the iso(thio)cyanate compound (B) and the alcohol compound (C) used in the mixing step are the same as the molar ratio [hydroxy group / iso(thio)cyanate group] and the total content of the iso(thio)cyanate compound (B) and the alcohol compound (C) in the monomer composition of the present disclosure.

[0108] In the mixing step, in addition to the components of the non-tin catalyst (A), the iso(thio)cyanate compound (B), and the alcohol compound (C), other components may also be added and mixed. As another component, a polymerization inhibitor (G) is preferable. For the polymerization inhibitor (G), the section "Monomer composition" can be referred to as appropriate. When the components are mixed in the mixing step with the addition of a polymerization inhibitor (G), the polymerization of the alcohol compound (C) can be further suppressed, and the reaction between the iso(thio)cyanate compound (B) and the alcohol compound (C) can proceed more effectively. The amount of the polymerization inhibitor (G) 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, based on the total amount of the non-tin catalyst (A), the iso(thio)cyanate compound (B), and the alcohol compound (C) used.

[0109] [Curable composition] The curable composition of the present disclosure contains the monomer composition of the present disclosure described above. That is, the curable composition of the present disclosure contains each of the components in the monomer composition of the present disclosure described above. The curable composition of the present disclosure may consist of the above-described monomer composition of the present disclosure (i.e., the monomer composition of the present disclosure itself).

[0110] The curable composition of the present disclosure is suitably used for producing a cured product (for example, a molded product described below). The term "cured product" used herein refers to a product obtained by curing the curable composition of the present disclosure. The curing of the curable composition of the present disclosure is achieved by polymerization of the contained monomers. Examples of methods for curing the curable composition of the present disclosure include a method of polymerizing the monomers in the curable composition at room temperature, a method of thermally polymerizing the monomers in the curable composition, and a method of photopolymerizing the monomers in the curable composition.

[0111] The hardenable composition of the present disclosure has a color suitable for dental materials when cured (for example, not yellowish). It is believed that the above-mentioned (meth)acrylate monomer (D) (that is, the (meth)acrylate monomer (D) containing a urethane bond) as a monomer contributes to such an effect.

[0112] The content of the monomer composition in the curable composition of the present disclosure is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total amount of the curable composition. The content of the monomer composition in the curable composition of the present disclosure may be 100% by mass, or may be 80% by mass or less, 60% by mass or less, 50% by mass or less, etc., relative to the total amount of the curable composition.

[0113] <Polymerization initiator> The curable composition of the present disclosure preferably contains a polymerization initiator. When the curable composition of the present disclosure contains a polymerization initiator, the polymerization initiator contained may be of only one type, or may be of two or more types. When the curable composition of the present disclosure contains a polymerization initiator, the polymerization of the monomer (i.e., the (meth)acrylate monomer (D) and other monomers contained as necessary; the same applies hereinafter) can be further promoted in the process of curing the curable composition.

[0114] When room temperature polymerization is carried out as the polymerization of the monomer, a preferred polymerization initiator is, for example, a redox-based polymerization initiator in which an oxidizing agent and a reducing agent are combined. When a redox-based polymerization initiator is used, for example, an oxidizing agent and a reducing agent may be prepared in separately packaged forms and mixed together immediately before use.

[0115] The oxidizing agent is not particularly limited, and examples thereof include organic peroxides, etc. Examples of organic peroxides include diacyl peroxides (e.g., benzoyl peroxide, etc.), peroxyesters (e.g., t-butyl peroxybenzoate, etc.), dialkyl peroxides (e.g., dicumyl peroxide, etc.), peroxyketals (e.g., 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, etc.), ketone peroxides (e.g., methyl ethyl ketone peroxide, etc.), and hydroperoxides (e.g., t-butyl hydroperoxide, etc.).

[0116] The reducing agent is not particularly limited, and a tertiary amine (for example, N,N-dimethylaniline, etc.) is usually used.

[0117] In addition to these organic peroxide / amine-based redox polymerization initiators, there are also cumene hydroperoxide / thiourea-based and ascorbic acid / Cu-based 2+ Examples include salt-based systems, organic peroxide / amine / sulfinic acid (or its salt)-based systems, etc. As the polymerization initiator, tributylborane, organic sulfinic acid, etc. may also be suitably used.

[0118] When thermal polymerization is carried out by heating to polymerize the monomer, the polymerization initiator is preferably a peroxide, an azo compound, or the like. The peroxide is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. The azo compound is not particularly limited, and examples thereof include azobisisobutyronitrile.

[0119] When photopolymerization is performed by irradiation with visible light to polymerize a monomer, the polymerization initiator (hereinafter also referred to as "photopolymerization initiator") is preferably a redox initiator such as α-diketone / tertiary amine, α-diketone / aldehyde, or α-diketone / mercaptan. The photopolymerization initiator is not particularly limited, and examples thereof include α-diketone / reducing agent, ketal / reducing agent, and thioxanthone / reducing agent. Examples of α-diketones include camphorquinone. An example of the ketal is benzyl dimethyl ketal. Examples of thioxanthone include 2-chlorothioxanthone. Examples of reducing agents include tertiary amines (such as Michler's ketone), aldehydes (such as citronellal), and compounds containing a thiol group (such as 2-mercaptobenzoxazole). Furthermore, polymerization initiators such as α-diketone / organic peroxide / reducing agent obtained by adding an organic peroxide to these redox initiators are also suitably used as photopolymerization initiators.

[0120] Examples of photopolymerization initiators for photopolymerization by ultraviolet irradiation include benzoin alkyl ether, benzil dimethyl ketal, and (bis)acylphosphine oxides.

[0121] Examples of the (bis)acylphosphine oxides include acylphosphine oxides (for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.), and bisacylphosphine oxides (for example, 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 be used in combination with the above-mentioned visible light photopolymerization initiators.

[0122] For example, a polymerization initiator may be used by referring to International Publication Nos. 2019 / 107323 and 2020 / 040141.

[0123] The content of the polymerization initiator is preferably from 0.01 to 20% by mass, and more preferably from 0.1 to 5% by mass, based on the total amount of monomers contained in the curable composition.

[0124] <Filler> The curable compositions of the present disclosure may contain a filler. When the curable composition of the present disclosure contains a filler, the filler contained may be of only one type, or may be of two or more types. When the curable composition of the present disclosure contains a filler, the mechanical properties of the cured product are further improved.

[0125] Fillers are broadly classified into organic fillers and inorganic fillers. The organic filler may be, for example, a fine powder of polymethyl methacrylate or the like.

[0126] Examples of materials for inorganic fillers include various types of glasses (for example, containing silicon dioxide as a main component and, as necessary, oxides of heavy metals, boron, aluminum, etc.), various types of ceramics, diatomaceous earth, kaolin, clay minerals (for example, montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, and hydroxyapatite. Specific examples of inorganic fillers include barium borosilicate glass, strontium boroaluminosilicate glass, lanthanum glass, fluoroaluminosilicate glass, and boroaluminosilicate glass.

[0127] As the filler, for example, fillers described in WO 2019 / 107323, WO 2020 / 040141, etc. may be used.

[0128] The content of the filler is preferably 10 parts by mass to 2000 parts by mass, more preferably 50 parts by mass to 1000 parts by mass, and even more preferably 100 parts by mass to 600 parts by mass, relative to 100 parts by mass of the total amount of the monomers contained in the curable composition.

[0129] <Other ingredients> The curable composition of the present disclosure may contain other components in addition to the components described above. Other ingredients include pigments, dyes, bactericides, disinfectants, stabilizers, preservatives, and the like.

[0130] <Preferred Use> There are no particular limitations on the uses of the curable composition of the present disclosure. The curable composition of the present disclosure can be used, for example, as a paint, a composition for forming a coating film, a dental material composition, etc.

[0131] The hardenable composition of the present disclosure is particularly suitable as a dental material composition because it can form a hardened product having a color suitable for a dental material. Here, the term "dental material composition" refers to a composition that can be used as a dental material, such as the dental material composition itself, a hardened product of the dental material composition (for example, a molded product described below), or a further processed product of the hardened product. Dental materials include dental restorative materials, denture base resins, denture base lining materials, impression materials, luting materials (e.g., resin cements, resin-added glass ionomer cements, etc.), dental adhesives (e.g., orthodontic adhesives, cavity application adhesives, etc.), fissure sealants, resin blocks for CAD (Computer Aided Design) / CAM (Computer Aided Manufacturing), temporary crowns, artificial tooth materials, etc. Examples of dental restorative materials include composite resins for crowns, composite resins for filling caries cavities, composite resins for core construction, and composite resins for filling and restoring.

[0132] <Example of manufacturing method> There are no particular limitations on the method for producing the curable composition of the present disclosure. An example of a method for producing the curable composition of the present disclosure will now be described. A method for producing the curable composition of the present disclosure includes, for example, the steps of preparing the monomer composition of the present disclosure and mixing the monomer composition with other components (e.g., a polymerization initiator, a filler, etc.). The method for producing the curable composition of the present disclosure may include other steps as needed.

[0133] [Molded body] The molded article of the present disclosure is a cured product of the above-described curable composition of the present disclosure. Therefore, the color of the molded article of the present disclosure is suitable for dental materials. The molded article is produced, for example, by molding the curable composition of the present disclosure into a desired shape and then curing it. Examples of methods for curing the curable composition of the present disclosure are described above. [Example]

[0134] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples.

[0135] The abbreviations for the compounds used in the examples of this disclosure are shown below. <Catalyst> (Non-tin catalyst (A)) ZDBDT: Zinc dibutyldithiocarbamate ZACAC: Zinc acetylacetonate InACAC: Indium acetylacetonate PtACAC: Platinum acetylacetonate PtTTPP: tetrakis(triphenylphosphine)platinum CuTTTF: Tris(triphenylphosphine)(trifluoromethyl)copper (tin-based catalyst) DBTDL: Dibutyltin dilaurate <Iso(thio)cyanate compound (B)> XDI: m-xylylene diisocyanate <Alcohol Compound (C)> HPA: 2-hydroxypropyl acrylate <Stabilizer (E)> (Compounds that do not contain at least one of a carboxylic acid amide group and a sulfonamide group) PhOH: Phenol HCl: Hydrochloric acid TPP: Triphenyl phosphite (Compounds containing at least one of a carboxylic acid amide group and a sulfonamide group) PTSA: p-toluenesulfonamide BzA: benzamide <Thiol Compound (F)> THIOL: 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 <Polymerization inhibitor (G)> BHT: Dibutylhydroxytoluene

[0136] [High-performance liquid chromatography (HPLC) measurement method] The HPLC chart spectra of the (meth)acrylates obtained in the examples and comparative examples of the present disclosure were measured using an HPLC device "LC-20AT" manufactured by Shimadzu Corporation. The (meth)acrylates obtained in the Examples, Comparative Examples, and Reference Examples of the present disclosure were dissolved in CH3CN, and then the (meth)acrylates were measured using an eluent of CH3CN / H2O=90 / 10.

[0137] [Hue determination] Regarding the color hue in the examples and comparative examples of the present disclosure, the color hue of the monomer compositions of Examples 3 to 16 and Comparative Examples 1 to 13 is *and b of the monomer composition of Example 1 or Example 2 * The difference between (Δb * Specifically, the b of the monomer compositions of Examples 3 and 4 and Comparative Examples 1 to 4, which do not contain a thiol compound (F) as a raw material for the monomer composition, is * The comparison object is the monomer composition b of Example 1, which does not contain a thiol compound (F) as a raw material for the monomer composition. * The monomer compositions of Examples 5 and 6 and Comparative Examples 5 to 8, which contain a thiol compound (F) as a raw material for the monomer composition, were * The comparison object is the monomer composition b of Example 2, which contains a thiol compound (F) as a raw material for the monomer composition. * The monomer compositions of Example 8 and Comparative Example 9, which contain a thiol compound (F) as a raw material for the monomer composition, were * The comparison object is the monomer composition b of Example 7, which contains a thiol compound (F) as a raw material for the monomer composition. * The monomer compositions of Example 10 and Comparative Example 10, which contain a thiol compound (F) as a raw material for the monomer composition, were * The comparison object is the monomer composition b of Example 9, which contains a thiol compound (F) as a raw material for the monomer composition. * The monomer compositions of Example 12 and Comparative Example 11, which contain a thiol compound (F) as a raw material for the monomer composition, were * The comparison object is the monomer composition b of Example 11 containing a thiol compound (F) as a raw material for the monomer composition. * The monomer compositions of Example 14 and Comparative Example 12, which contain a thiol compound (F) as a raw material for the monomer composition, were * The comparison object is the monomer composition b of Example 13 containing a thiol compound (F) as a raw material for the monomer composition. * The monomer compositions of Example 16 and Comparative Example 13, which contain a thiol compound (F) as a raw material for the monomer composition, were * The comparison object is the monomer composition b of Example 15 containing a thiol compound (F) as a raw material for the monomer composition. * It was decided. Regarding the hue in the reference examples of the present disclosure, the b *and b of the monomer compositions of Reference Examples 1 and 2 * The difference between (Δb * The monomer composition of Reference Example 3, which does not contain a thiol compound (F) as a raw material for the monomer composition, is defined by the formula b. * The comparison object is the monomer composition b of Reference Example 1, which does not contain a thiol compound (F) as a raw material for the monomer composition. * The monomer composition b of Reference Example 4 containing the thiol compound (F) as a raw material for the monomer composition was * The comparison object is the monomer composition b of Reference Example 2, which contains a thiol compound (F) as a raw material for the monomer composition. * It was decided. Δb * If Δb is less than 0.3, the judgment is "A", * Those with a value of 0.3 or more were rated "B".

[0138] (b * (Method of measurement) b in the monomer compositions of the examples and comparative examples of the present disclosure * was measured using a spectrophotometer (SD-3000 manufactured by Nippon Denshoku Co., Ltd.) and the temperature was controlled at 25°C.

[0139] [Manufacturing example: XDI] An XDI product (manufactured by Tokyo Chemical Industry Co., Ltd., product code: "X0022", XDI purity: >98.0% (GC)) was charged into a still equipped with a capillary tube connected to a nitrogen line. Vacuum distillation was then carried out in the pressure range of 0.5 to 5 torr (66.7 Pa to 666.7 Pa) and the temperature range of 160°C to 240°C. The distillate was then collected. XDI was thus obtained from the XDI product.

[0140] [Example 1] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 41.97 parts by weight of XDI, 0.1 parts by weight of ZDBDT, and 0.05 parts by weight of BHT. After dissolving to form a homogeneous solution, the solution was heated to 80°C, and 58.03 parts by weight of HPA was added dropwise over 1 hour. Since the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled to keep the temperature below 90°C. After the entire HPA was added dropwise, the reaction temperature was maintained at 90°C and the reaction was allowed to proceed for 6 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing urethane acrylate monomer (A-1).

[0141] [Example 2] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 42.70 parts by weight of XDI, 0.1 parts by weight of ZDBDT, 0.05 parts by weight of BHT, and 4.18 parts by weight of THIOL. The mixture was dissolved to form a homogeneous solution and then reacted at 80°C for 4 hours. The solution was heated to 90°C, and 53.12 parts by weight of HPA was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 90°C. After the entire amount was added, the reaction temperature was maintained at 90°C and the reaction was continued for 6 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing thiourethane acrylate monomer (A-2).

[0142] [Example 3] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 41.97 parts by weight of XDI, 0.1 parts by weight of ZDBDT, 0.05 parts by weight of BHT, 0.025 parts by weight of PhOH, and 0.025 parts by weight of HCl. After dissolving to form a homogeneous solution, the solution was heated to 80°C, and 58.03 parts by weight of HPA was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 90°C. After the entire HPA was added dropwise, the reaction temperature was maintained at 90°C and the reaction was allowed to proceed for 6 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing urethane acrylate monomer (B-1).

[0143] [Example 4] 100 g of a monomer composition containing a urethane acrylate monomer (B-2) was obtained in the same manner as in Example 3, except that PhOH and HCl were changed to 0.05 parts by mass of TPP.

[0144] [Example 5] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 42.70 parts by weight of XDI, 0.1 parts by weight of ZDBDT, 0.05 parts by weight of BHT, 0.025 parts by weight of PhOH, 0.025 parts by weight of HCl, and 4.18 parts by weight of THIOL. After dissolving to form a homogeneous solution, the mixture was reacted at 80°C for 4 hours. The solution was heated to 90°C, and 53.12 parts by weight of HPA was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 90°C. After the entire amount was added, the reaction temperature was maintained at 90°C and the reaction was continued for 6 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing thiourethane acrylate monomer (B-3).

[0145] [Example 6] 100 g of a monomer composition containing a thiourethane acrylate monomer (B-4) was obtained in the same manner as in Example 5, except that PhOH and HCl were changed to 0.05 parts by mass of TPP.

[0146] [Examples 7 to 16] The procedure of Example 5 was repeated except that the non-tin catalyst (A) and stabilizer (E) were changed as shown in Table 1, to obtain 100 g of a monomer composition.

[0147] [Comparative Example 1] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 41.97 parts by weight of XDI, 0.1 parts by weight of ZDBDT, 0.05 parts by weight of BHT, and 0.05 parts by weight of PTSA. After dissolving to form a homogeneous solution, the solution was heated to 80°C, and 58.03 parts by weight of HPA was added dropwise over 1 hour. Since the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled to keep the temperature below 90°C. After the entire HPA was added dropwise, the reaction temperature was maintained at 90°C and the reaction was allowed to proceed for 6 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing urethane acrylate monomer (C-1).

[0148] Comparative Example 2 100 g of a monomer composition containing a urethane acrylate monomer (C-2) was obtained in the same manner as in Comparative Example 1, except that PTSA was changed to BzA.

[0149] Comparative Example 3 100 g of a monomer composition containing a urethane acrylate monomer (C-3) was obtained in the same manner as in Comparative Example 1, except that the amount of PTSA was changed from 0.05 parts by mass to 0.005 parts by mass.

[0150] Comparative Example 4 100 g of a monomer composition containing a urethane acrylate monomer (C-4) was obtained in the same manner as in Comparative Example 2, except that the amount of BzA was changed from 0.05 parts by mass to 0.005 parts by mass.

[0151] Comparative Example 5 A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 42.70 parts by weight of XDI, 0.1 parts by weight of ZDBDT, 0.05 parts by weight of BHT, 0.05 parts by weight of PTSA, and 4.18 parts by weight of THIOL. The mixture was dissolved to form a homogeneous solution and then reacted at 80°C for 4 hours. The solution was heated to 90°C, and 53.12 parts by weight of HPA was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 90°C. After the entire amount was added, the reaction temperature was maintained at 90°C and the reaction was continued for 6 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing thiourethane acrylate monomer (C-5).

[0152] Comparative Example 6 100 g of a monomer composition containing a thiourethane acrylate monomer (C-6) was obtained in the same manner as in Comparative Example 5, except that PTSA was changed to BzA.

[0153] Comparative Example 7 100 g of a monomer composition containing a thiourethane acrylate monomer (C-7) was obtained in the same manner as in Comparative Example 5, except that the amount of PTSA was changed from 0.05 parts by mass to 0.005 parts by mass.

[0154] [Comparative Example 8] 100 g of a monomer composition containing a thiourethane acrylate monomer (C-8) was obtained in the same manner as in Comparative Example 6, except that the amount of BzA was changed from 0.05 parts by mass to 0.005 parts by mass.

[0155] [Comparative Examples 9 to 13] The procedure of Comparative Example 5 was repeated except that the non-tin catalyst (A) and stabilizer (E) were changed as shown in Table 1, to obtain 100 g of a monomer composition.

[0156] [Reference example 1] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 41.97 parts by weight of XDI, 0.1 parts by weight of DBTDL, and 0.05 parts by weight of BHT. After dissolving to form a homogeneous solution, the solution was heated to 80°C, and 58.03 parts by weight of HPA was added dropwise over 1 hour. Since the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled to keep the temperature below 90°C. After the entire HPA was added dropwise, the reaction temperature was maintained at 90°C and the reaction was allowed to proceed for 4 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor, yielding 100 g of a monomer composition containing urethane acrylate monomer (D-1).

[0157] [Reference example 2] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 42.70 parts by weight of XDI, 0.1 parts by weight of DBTDL, 0.05 parts by weight of BHT, and 4.18 parts by weight of THIOL. The mixture was dissolved to form a homogeneous solution and then reacted at 80°C for 2 hours. The solution was heated to 90°C, and 53.12 parts by weight of HPA was added dropwise over 1 hour. The internal temperature rose due to the heat of reaction during the addition, so the amount added was controlled to keep the temperature below 90°C. After the entire amount was added, the reaction temperature was maintained at 90°C and the reaction was continued for 4 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing thiourethane acrylate monomer (D-2).

[0158] [Reference example 3] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 41.97 parts by weight of XDI, 0.1 parts by weight of DBTDL, 0.05 parts by weight of BHT, and 0.05 parts by weight of PTSA. After dissolving to form a homogeneous solution, the solution was heated to 80°C, and 58.03 parts by weight of HPA was added dropwise over 1 hour. During the dropwise addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 90°C. After the entire HPA was added dropwise, the reaction temperature was maintained at 90°C and the reaction was allowed to proceed for 4 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing urethane acrylate monomer (E-1).

[0159] [Reference example 4] A 100 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 42.70 parts by weight of XDI, 0.1 parts by weight of DBTDL, 0.05 parts by weight of BHT, 0.05 parts by weight of PTSA, and 4.18 parts by weight of THIOL. The mixture was dissolved to form a homogeneous solution and then reacted at 80°C for 2 hours. The solution was heated to 90°C, and 53.12 parts by weight of HPA was added dropwise over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 90°C. After the entire amount was added, the reaction temperature was maintained at 90°C and the reaction was continued for 4 hours. The progress of the reaction was monitored by HPLC analysis to confirm the end point. The product was discharged from the reactor to obtain 100 g of a monomer composition containing thiourethane acrylate monomer (E-2).

[0160] b of the monomer compositions of Examples 1 to 16, Comparative Examples 1 to 13, and Reference Examples 1 to 4 * Measurement results, Δb * The calculation results and the evaluation results of the hue of the monomer composition are shown in Tables 1 and 2.

[0161] [Table 1]

[0162] [Table 2]

[0163] In Tables 1 and 2, "amide-free compounds" refer to compounds that do not contain at least one of a carboxylic acid amide group and a sulfonamide group. In Tables 1 and 2, "amide-containing compounds" refer to compounds that contain at least one of a carboxylic acid amide group and a sulfonamide group.

[0164] UDMA (dimethacryloxyethyl 2,2,4-trimethylhexamethylenediurethane) and TEGDMA (triethylene glycol dimethacrylate), which are commonly used as monomers for dental materials, are b * However, the color is 0.5 or less, and other monomers for dental materials are also required to have a color of at least the same level. In this regard, the monomer compositions of Comparative Examples 1 to 4 contain a non-tin catalyst (A) and a urethane acrylate monomer (D) which is a reaction product of XDI (B) and HPA (C), but the content of the amide-containing compound was 1 mass ppm or more relative to the total amount of the monomer composition. The monomer compositions of Comparative Examples 5 to 13 contain a non-tin catalyst (A) and a thiourethane acrylate (D) which is a reaction product of XDI (B), HPA (C), and THIOL (F), but the content of the amide-containing compound was 1 mass ppm or more relative to the total amount of the monomer composition. Therefore, all of the b * was more than 0.5. The hues of the monomer compositions of Comparative Examples 1 to 13 were yellowish when visually observed. In other words, it was found that the monomer compositions of Comparative Examples 1 to 13 were not suitable for dental use. In contrast, the monomer compositions of Examples 1, 3, and 4 each contained a non-tin catalyst (A) and a urethane acrylate (D) that is a reaction product of XDI (B) and HPA (C), and the content of the amide-containing compound was less than 1 ppm by mass relative to the total amount of the monomer composition. The monomer compositions of Examples 2 and 5 to 16 each contained a non-tin catalyst (A) and a thiourethane acrylate (D) that is a reaction product of XDI (B), HPA (C), and THIOL (F), and the content of the amide-containing compound was less than 1 ppm by mass relative to the total amount of the monomer composition. Therefore, all of the b of the monomer compositions of Examples 1 to 16 * was 0.5 or less. The hues of the monomer compositions of Examples 1 to 16 were not yellowish when visually observed. That is, it was found that all of the monomer compositions of Examples 1 to 16 had hues suitable for dental materials. The monomer compositions of Reference Examples 1 to 4 contain a urethane acrylate monomer or a thiourethane acrylate monomer synthesized using DBTDL, a tin-based catalyst. Among these, the monomer compositions of Reference Examples 3 and 4 contain an amide-containing compound in an amount of 1 ppm by mass or more relative to the total amount of the monomer composition, but * The monomer compositions of Reference Examples 3 and 4 had a hue difference Δb * There was almost no difference. From these findings, it was found that the problem of the synthesized monomer composition having a yellowish hue when synthesizing a urethane (meth)acrylate monomer or a thiourethane (meth)acrylate monomer is a problem specific to the use of a non-tin catalyst, and that this problem can be solved by using an amide-containing compound at less than 1 ppm by mass.

[0165] The disclosure of Japanese Patent Application No. 2021-010402, filed on January 26, 2021, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A monomer composition comprising a non-tin catalyst (A) and a (meth)acrylate monomer (D) which is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (C), the content of an amide compound containing at least one of a carboxylic acid amide group and a sulfonamide group is less than 1 ppm by mass based on the total amount of the monomer composition, The non-tin catalyst (A) contains a ligand, the ligand includes a group having at least one of a diketone structure and a double bond other than a carbonyl bond, A monomer composition for use in dental materials.

2. A monomer composition comprising a non-tin catalyst (A) and a (meth)acrylate monomer (D) which is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (C), the content of an amide compound containing at least one of a carboxylic acid amide group and a sulfonamide group is less than 1 ppm by mass based on the total amount of the monomer composition, The non-tin catalyst (A) contains a ligand, the ligand includes a group having at least one of a diketone structure and a double bond other than a carbonyl bond, A monomer composition, wherein when the non-tin-based catalyst (A) contains a zinc-based catalyst, the zinc-based catalyst contains at least one of compounds represented by the following formula (X) and the following formula (Z): 【Chemistry 1】 (In formula (X), R X1 and R X2 are each independently a monovalent hydrocarbon group. M X is a zinc atom. n X is the valence of M X . A plurality of R X1 and R X2 may be the same or different.) 【Chemistry 2】 (In formula (Z), R Z1 is a halogen atom. M Z is a zinc atom. n Z is the valence of M Z . m Z is an integer of 1 or 0.)

3. The monomer composition according to claim 1 or claim 2, wherein the non-tin-based catalyst (A) comprises at least one of a compound represented by the following formula (X), a compound represented by the following formula (Y), and a compound represented by the following formula (Z): 【Chemistry 3】 (In formula (X), R Ｘ１ and R Ｘ２ are each independently a monovalent hydrocarbon group. Ｘ is a metal atom other than tin. Ｘ M Ｘ The valence of R Ｘ１ and R Ｘ２ may be the same or different.) 【Chemistry 4】 (In formula (Y), R Ｙ１ and R Ｙ２ are each independently a monovalent hydrocarbon group. Ｙ is a metal atom other than tin. Ｙ M Ｙ The valence of R Ｙ１ and R Ｙ２ may be the same or different.) 【Chemistry 5】 (In formula (Z), R Ｚ１ is a halogen atom. Ｚ is a metal atom other than tin. Ｚ M Ｚ is the valence of m Ｚ is an integer of 1 or 0.

4. The non-tin catalyst (A) contains a metal atom other than tin, The metal atom other than tin is an atom of a metal element belonging to any one of Periods 4 to 6 and Groups 4 to 14 (excluding tin atoms). The monomer composition according to any one of claims 1 to 3.

5. The monomer composition according to any one of claims 1 to 4, wherein the non-tin-based catalyst (A) comprises at least one selected from the group consisting of zinc-based catalysts, copper-based catalysts, indium-based catalysts, and platinum-based catalysts.

6. The monomer composition according to any one of claims 1 to 5, wherein the iso(thio)cyanate compound (B) contains an aromatic ring.

7. The monomer composition according to any one of claims 1 to 6, wherein the iso(thio)cyanate compound (B) comprises an iso(thio)cyanate compound (b1) not containing a thiourethane bond, or a reaction product (X) of an iso(thio)cyanate compound (b2) not containing a thiourethane bond with a thiol compound (F) containing two or more mercapto groups.

8. The monomer composition according to claim 7, wherein each of the iso(thio)cyanate compound (b1) and the iso(thio)cyanate compound (b2) contains at least one selected from the group consisting of m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate.

9. The monomer composition according to any one of claims 1 to 8, wherein the alcohol compound (C) comprises at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, ethylene glycol, and glycerin.

10. The monomer composition according to any one of claims 1 to 9, further comprising a stabilizer (E) which is at least one of a phosphite compound and a phenol compound.

11. The iso(thio)cyanate compound (B) is a reaction product of an iso(thio)cyanate compound (b2) not containing a thiourethane bond and a thiol compound (F) containing two or more mercapto groups. The monomer composition according to any one of claims 1 to 10.

12. A curable composition comprising the monomer composition according to any one of claims 1 to 11.

13. The curable composition of claim 12 further comprising a polymerization initiator.

14. The hardenable composition according to claim 12 or 13, which is a dental material composition.

15. A molded article which is a cured product of the hardenable composition according to any one of claims 12 to 14 and which is a dental material.

16. A method for producing a monomer composition containing a non-tin catalyst (A) and a (meth)acrylate monomer (D) which is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (C), comprising the steps of: The method includes a step of mixing the non-tin catalyst (A), the iso(thio)cyanate compound (B), and the alcohol compound (C), the content of an amide compound containing at least one of a carboxylic acid amide group and a sulfonamide group is less than 1 ppm by mass based on the total amount of the monomer composition; The non-tin catalyst (A) contains a ligand, the ligand includes a group having at least one of a diketone structure and a double bond other than a carbonyl bond, A method for producing a monomer composition, wherein when the non-tin-based catalyst (A) contains a zinc-based catalyst, the zinc-based catalyst contains at least one of compounds represented by the following formula (X) and the following formula (Z). 【Chemistry 6】 (In formula (X), R X1 and R X2 are each independently a monovalent hydrocarbon group. M X is a zinc atom. n X is the valence of M X . A plurality of R X1 and R X2 may be the same or different.) 【Chemistry 7】 (In formula (Z), R Z1 is a halogen atom. M Z is a zinc atom. n Z is the valence of M Z . m Z is an integer of 1 or 0.)

17. A method for producing a monomer composition containing a non-tin catalyst (A) and a (meth)acrylate monomer (D) which is a reaction product of an iso(thio)cyanate compound (B) and an alcohol compound (C), comprising the steps of: The method includes a step of mixing the non-tin catalyst (A), the iso(thio)cyanate compound (B), and the alcohol compound (C), the content of an amide compound containing at least one of a carboxylic acid amide group and a sulfonamide group is less than 1 ppm by mass based on the total amount of the monomer composition; The non-tin catalyst (A) contains a ligand, the ligand includes a group having at least one of a diketone structure and a double bond other than a carbonyl bond, The method for producing a monomer composition, wherein the monomer composition is used for a dental material.

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