Urethane (METH)acrylate compound, monomer composition, and photocurable composition and applications thereof

Abstract

Provided is a urethane (meth)acrylate compound represented by formula (1). The two R1 moieties are organic groups; the n X moieties are each independently a group represented by formula (X1); the (n+1) Y moieties are each independently a group represented by formula (Y1) or formula (Y2); the two R2 moieties are each independently a hydrogen atom or a methyl group; n is 1-10; RXA is a hydrocarbon group having a cyclic structure; the (m+k) RXB moieties are each independently a hydrocarbon group; m and k are each independently a numerical value of 1-5; the two RY1A moieties are each independently a C1-C5 linear alkylene group or a methylmethylene group; RY1B is a C5-C12 cyclic hydrocarbon group; and RY2A is a C5-C12 alicyclic hydrocarbon group.

Description

Urethane (meth)acrylate compound, monomer composition, photocurable composition, and application thereof

[0001] The present disclosure relates to a urethane (meth)acrylate compound, a monomer composition, and a photocurable composition and applications thereof (specifically, three-dimensional objects, medical device components, instruments used in the oral cavity, denture bases, surgical components, cured products, and dental materials).

[0002] In recent years, dental products and other devices to be worn in the oral cavity have been studied. For example, from the viewpoint of the efficiency of molding these dental products, a method for manufacturing three-dimensional objects such as dental products by stereolithography using a 3D printer is known (see, for example, Patent Document 1).

[0003] Conventionally, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (hereinafter also referred to as "UDMA") has been mainly used as a monomer in photocurable compositions for dental materials (see, for example, Patent Document 2).

[0004] Patent Document 1: Japanese Patent No. 4160311 Patent Document 2: Japanese Patent Laid-Open No. 2002-087921

[0005] Three-dimensional objects manufactured by stereolithography (e.g., instruments worn in the oral cavity, medical device components, denture bases, and surgical components) require mechanical properties such as toughness. Urethane dimethacrylate (specifically, the aforementioned UDMA) has traditionally been used as a material for stereolithography. However, when UDMA is used as a material for stereolithography, there is room for improvement in terms of the toughness of the resulting three-dimensional objects.

[0006] Furthermore, high bending strength is sometimes required for the cured product of the photocurable composition (for example, a dental material). However, photocurable compositions containing UDMA have room for improvement in terms of bending strength of the cured product.

[0007] The problem to be solved by a first aspect of the present disclosure is to provide a urethane (meth)acrylate compound, a monomer composition, and a photocurable composition suitable for obtaining a three-dimensionally shaped object having excellent toughness, as well as a three-dimensionally shaped object, an instrument used in the oral cavity, a medical device component, a denture base, and a surgical component having excellent toughness. The problem to be solved by a second aspect of the present disclosure is to provide a photocurable composition capable of obtaining a cured product having excellent bending strength, as well as a cured product and a dental material having excellent bending strength.

[0008] Specific means for solving the above problems are as follows. Below, <1> to <13> are the first aspect, and <6> and <14> to <19> are the second aspect. <6> is common to the first and second aspects.

[0009] <1> A urethane (meth)acrylate compound represented by the following formula (1):

[0010]

[0011] In formula (1), two R １ are each independently a divalent organic group, n Xs are each independently a divalent group represented by formula (X1), (n+1) Ys are each independently a divalent group represented by formula (Y1) or formula (Y2), and two R ２ are each independently a hydrogen atom or a methyl group, and n is an integer of 1 to 10. In formula (X1), R ＸＡ is a divalent hydrocarbon group containing a cyclic structure, and (m+k) R ＸＢ are each independently a divalent hydrocarbon group, m and k are each independently an integer of 1 to 5, and two *'s each indicate a bonding position. Ｙ１Ａ are each independently a linear alkylene group having 1 to 5 carbon atoms or a methylmethylene group, and R Ｙ１Ｂ is a divalent cyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position. Ｙ２Ａ is a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position.

[0012] <2> The urethane (meth)acrylate compound according to claim 1, wherein the divalent group represented by formula (Y1) is a divalent group represented by any one of the following formulas (Y1-1) to (Y1-7):

[0013]

[0014] In each of formulas (Y1-1) to (Y1-7), two * each indicate a bonding position.

[0015] <3> The urethane (meth)acrylate compound according to <1> or <2>, having a molecular weight of 12,000 or less. <4> A monomer composition comprising the urethane (meth)acrylate compound according to any one of <1> to <3>. <5> The monomer composition according to <4>, which is a monomer composition for use as a material for an instrument worn in the oral cavity, a monomer composition for use as a material for a medical device component, a monomer composition for use as a material for a denture base, or a monomer composition for use as a material for a surgical component. <6> A photocurable composition comprising the urethane (meth)acrylate compound according to any one of <1> to <3> and a polymerization initiator. <7> The photocurable composition according to <6>, which is used for producing a three-dimensional object by stereolithography. <8> The photocurable composition according to <6> or <7>, which is used for producing an instrument worn in the oral cavity, a component for a medical device, a denture base, or a surgical component. <9> A three-dimensional object made from the photocurable composition according to any one of <6> to <8>. <10> An instrument used in the oral cavity, comprising the three-dimensionally shaped object according to <9>. <11> A medical device component, comprising the three-dimensionally shaped object according to <9>. <12> A denture base, comprising the three-dimensionally shaped object according to <9>. <13> A surgical component, comprising the three-dimensionally shaped object according to <9>. <14> The photocurable composition according to <6>, further comprising a filler. <15> The photocurable composition according to <14>, wherein the content of the filler is 40% by mass to 90% by mass, based on the total amount of the photocurable composition. <16> The photocurable composition according to any one of <6>, <14>, and <15>, wherein the viscosity measured using an E-type viscometer at 50 rpm and 80°C is 10 mPa·s to 50,000 mPa·s. <17> The photocurable composition according to any one of <6> and <14> to <16>, which is a photocurable composition for use as a dental material. <18> A cured product of the photocurable composition according to any one of <6> and <14> to <17>. <19> A dental material comprising the photocurable composition according to <6> and <14> to <17> or a cured product thereof.

[0016] According to a first aspect of the present disclosure, there are provided a urethane (meth)acrylate compound, a monomer composition, and a photocurable composition suitable for obtaining a three-dimensionally shaped object having excellent toughness, as well as a three-dimensionally shaped object, an instrument for use in an oral cavity, a medical device component, a denture base, and a surgical component having excellent toughness. According to a second aspect of the present disclosure, there are provided a photocurable composition capable of obtaining a cured product having excellent bending strength, as well as a cured product and a dental material having excellent bending strength.

[0017] In this disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In this disclosure, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In this disclosure, when multiple substances corresponding to each component exist, the amount of each component refers to the total amount of multiple substances unless otherwise specified. In this disclosure, "(meth)acryloyl group" means acryloyl group and methacryloyl group, and "(meth)acrylate" means acrylate and methacrylate. In this disclosure, "*" in a chemical formula indicates a bonding position. In this disclosure, "light" means visible light or ultraviolet light.

[0018] The first and second aspects of the present disclosure will be described below in order. There may be overlapping features between the first and second aspects. That is, one of the first and second aspects may satisfy the characteristics of the other. Therefore, as preferred features of either the first or second aspect, the features of the other may be referenced as appropriate.

[0019] First Aspect A first aspect of the present disclosure will be described below.

[0020] [Urethane (meth)acrylate Compound] The urethane (meth)acrylate compound in the first embodiment is a urethane (meth)acrylate compound represented by the following formula (1).

[0021]

[0022] In formula (1), two R １are each independently a divalent organic group, n Xs are each independently a divalent group represented by formula (X1), (n+1) Ys are each independently a divalent group represented by formula (Y1) or formula (Y2), and two R ２ are each independently a hydrogen atom or a methyl group, and n is an integer of 1 to 10. In formula (X1), R ＸＡ is a divalent hydrocarbon group containing a cyclic structure, and (m+k) R ＸＢ are each independently a divalent hydrocarbon group, m and k are each independently an integer of 1 to 5, and two *'s each indicate a bonding position. Ｙ１Ａ are each independently a linear alkylene group having 1 to 5 carbon atoms or a methylmethylene group, and R Ｙ１Ｂ is a divalent cyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position. Ｙ２Ａ is a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position.

[0023] The urethane (meth)acrylate compound according to the first aspect is suitable for obtaining a three-dimensionally shaped object having excellent toughness. Specifically, a three-dimensionally shaped object (e.g., a stereolithography object) produced using the urethane (meth)acrylate compound according to the first aspect exhibits excellent toughness compared to a three-dimensionally shaped object produced using conventional UDMA. The effect of improving the toughness of the three-dimensionally shaped object is believed to be due to the structure of formula (1) above, which includes a urethane bond (—NH(C═O)O— bond), X containing a cyclic structure, and Y containing a cyclic structure. Furthermore, a three-dimensionally shaped object (e.g., a stereolithography object) produced using the urethane (meth)acrylate compound according to the first aspect exhibits a flexural modulus equivalent to that of a three-dimensionally shaped object produced using conventional UDMA.

[0024] In formula (1), two R １ are each independently a divalent organic group. １ is preferably a divalent hydrocarbon group, more preferably an alkylene group. １The number of carbon atoms in the divalent hydrocarbon group represented by the formula (1) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. ２ are each independently a hydrogen atom or a methyl group.

[0025] The moieties at both ends of the urethane (meth)acrylate compound represented by formula (1) are groups represented by the following formula (1E): The groups represented by the following formula (1E) (i.e., the moieties at both ends in formula (1)) can be formed using a hydroxy group-containing (meth)acrylate compound (specifically, a compound represented by the following formula (1EM)) for forming the moieties at both ends in formula (1).

[0026]

[0027] R in formula (1E) and formula (1EM) １ and R ２ are R in formula (1), respectively. １ and R ２ is synonymous with.

[0028] In formula (1), n ​​X's are each independently a divalent group represented by formula (X1). ＸＡ is a divalent hydrocarbon group containing a cyclic structure, and (m+k) R ＸＢ are each independently a divalent hydrocarbon group, m and k are each independently an integer of 1 to 5, and two * symbols each indicate a bonding position.

[0029] In formula (X1), R ＸＡ The divalent hydrocarbon group having a cyclic structure represented by the formula (X1-1) is preferably an arylene group having 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms) or an arylene alkylene arylene group having 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms), more preferably an arylene alkylene arylene group having 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms), and even more preferably a divalent hydrocarbon group represented by either of the following formula (X1-1) or (X1-2) (* indicates a bonding position).

[0030]

[0031] In formula (X1), R ＸＢ The divalent hydrocarbon group represented by the formula (I) is preferably a linear or branched alkylene group, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms), and even more preferably an ethylene group or a methylethylene group.

[0032] X in formula (1) (i.e., the divalent group represented by formula (X1)) can be formed using a diol compound for forming X in formula (1) (more specifically, a compound in which a hydroxy group is bonded to each of the two * positions in the divalent group represented by formula (X1)). Examples of diol compounds for forming X in formula (1) include: bisphenol A-propylene oxide 2-4 mol adduct, bisphenol A-propylene oxide 2-5 mol adduct, bisphenol A-propylene oxide 2-9 mol adduct, bisphenol F-propylene oxide 2-5 mol adduct, and the like.

[0033] In formula (1), (n+1) Ys are each independently a divalent group represented by formula (Y1) or formula (Y2).

[0034] In formula (Y1), two R Ｙ１Ａ are each independently a linear alkylene group having 1 to 5 carbon atoms or a methylmethylene group, and R Ｙ１Ｂ is a divalent cyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position.

[0035] In formula (Y1), R Ｙ１Ｂ The divalent cyclic hydrocarbon group having 5 to 12 carbon atoms represented by the formula (Y1B-1) is preferably a divalent group represented by any one of the following formulae (Y1B-1) to (Y1B-6).

[0036]

[0037] In each of formulae (Y1B-1) to (Y1B-6), two * indicate the bonding position.

[0038] In formula (Y1), R Ｙ１Ａ are preferably each independently a methylene group or a methylmethylene group.

[0039] The divalent group represented by formula (Y1) is preferably a divalent group represented by any one of the following formulae (Y1-1) to (Y1-7).

[0040]

[0041] In each of formulas (Y1-1) to (Y1-7), two * each indicate a bonding position.

[0042] In formula (Y2), R Ｙ２Ａ The divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms represented by the formula (Y2A-1) is preferably a divalent group represented by any one of the following formulae (Y2A-1) to (Y2A-6).

[0043]

[0044] Y in formula (1) (i.e., a divalent group represented by either formula (Y1) or formula (Y2)) can be formed using a diisocyanate compound corresponding to Y in formula (1) (specifically, a compound in which an isocyanate group is bonded to each of the two * positions in the divalent group represented by either formula (Y1) or formula (Y2)).

[0045] The molecular weight of the urethane (meth)acrylate compound in the first embodiment (i.e., the urethane (meth)acrylate compound represented by formula (1)) is not particularly limited, but is preferably not more than 24,000, more preferably not more than 12,000, and preferably not more than 8,000. The lower limit of the molecular weight of the urethane (meth)acrylate compound in the first embodiment is not particularly limited as long as formula (1) is satisfied, but examples of the lower limit of the molecular weight include 600 and 800.

[0046] <Example of Production Method for Urethane (Meth)acrylate Compound in First Aspect (Production Method X)> Hereinafter, an example of a production method (hereinafter also referred to as "Production Method X") for producing the urethane (meth)acrylate compound in the first aspect (i.e., the urethane (meth)acrylate compound represented by formula (1)) will be described.

[0047] Production method X includes a step of reacting the above-mentioned "hydroxy group-containing (meth)acrylate compound for forming both terminal moieties in formula (1)", the above-mentioned "diol compound for forming X in formula (1)", and the above-mentioned "diisocyanate compound corresponding to Y in formula (1)", to produce a urethane (meth)acrylate compound represented by formula (1), which is a reaction product of these compounds (hereinafter also referred to as "raw materials"). Production method X may include other steps as necessary.

[0048] The reaction in Production Method X may be carried out in a solvent or without a solvent. Any known solvent can be used as long as it is inert to the reaction. Examples of the solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and perclene; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used alone or in combination.

[0049] (Catalyst) A catalyst may be used in the above reaction in Production Method X. Examples of the catalyst include: organotin compounds such as dibutyltin dilaurate (also known as dibutyltin dilaurate), dibutyltin dioctate, and tin octoate; organometallic compounds other than tin compounds such as copper naphthenate, cobalt naphthenate, zinc naphthenate, zirconium acetylacetonate, iron acetylacetonate, and germanium acetylacetonate; amine compounds such as triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undecene, N,N-dimethylcyclohexylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-pentamethyldiethylenetriamine, N,N,N',N'-tetra(3-dimethylaminopropyl)-methanediamine, N,N'-dimethylpiperazine, and 1,2-dimethylimidazole, and salts thereof; trialkylphosphine compounds such as tri-n-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine, and tri-n-octylphosphine; and the like. Of these, dibutyltin dilaurate and tin octoate are preferred.

[0050] The amount of the catalyst used may be 0.001% by mass to 1.0% by mass, or may be 0.01% by mass to 0.5% by mass, based on the total of the aforementioned "hydroxy group-containing (meth)acrylate compound for forming both terminal moieties in formula (1)", the aforementioned "diol compound for forming X in formula (1)", and the aforementioned "diisocyanate compound corresponding to Y in formula (1)".

[0051] The reaction temperature is not particularly limited and is, for example, 20°C to 170°C, preferably 30°C to 140°C, and more preferably 50°C to 120°C.

[0052] The reaction time is not particularly limited as it depends on conditions such as the reaction temperature, and is, for example, 5 minutes to 50 hours. The end point of the reaction can be confirmed by analysis by HPLC (high performance liquid chromatography), etc.

[0053] A polymerization inhibitor may be used during the above reaction in Production Method X. Examples of the polymerization inhibitor include dibutylhydroxytoluene (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), and phenothiazine (PTZ).

[0054] The amount of the polymerization inhibitor used may be 0.001% by mass to 0.5% by mass, 0.002% by mass to 0.3% by mass, or 0.005% by mass to 0.3% by mass, relative to the total of the aforementioned "hydroxy group-containing (meth)acrylate compound for forming both terminal moieties in formula (1)", the aforementioned "diol compound for forming X in formula (1)", and the aforementioned "diisocyanate compound corresponding to Y in formula (1)".

[0055] [Monomer composition] The monomer composition according to the first embodiment contains the urethane(meth)acrylate compound according to the first embodiment (i.e., the urethane(meth)acrylate compound represented by formula (1)). The monomer composition according to the first embodiment may contain only one type of urethane(meth)acrylate compound represented by formula (1), or may contain two or more types of urethane(meth)acrylate compounds represented by formula (1) (for example, two or more types of compounds in which at least one of x, y, and n in formula (1) is different).

[0056] The monomer composition in the first aspect contains the urethane (meth)acrylate compound in the first aspect, and therefore exhibits the effect of the urethane (meth)acrylate compound in the first aspect (i.e., the effect of being suitable for imparting toughness to the cured product).

[0057] The content of the urethane (meth)acrylate compound in the first embodiment relative to the total amount of the monomer composition in the first embodiment may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, 80% by mass or more, or 90% by mass or more. The upper limit of the content of the urethane (meth)acrylate compound in the first embodiment relative to the total amount of the monomer composition in the first embodiment may be, for example, 99% by mass, 95% by mass, or 90% by mass. For example, the monomer composition in the first embodiment may be a composition consisting of the urethane (meth)acrylate compound in the first embodiment in a content of 90% by mass or more and impurities.

[0058] The monomer composition in the first embodiment may also contain at least one other (meth)acrylate compound other than the urethane (meth)acrylate compound in the first embodiment.

[0059] Other (meth)acrylate compounds include, for example, neopentyl di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol 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 glycol di(meth)acrylate ... ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (urethane dimethacrylate: UDMA), benzyl (meth)acrylate, m-phenoxybenzyl acrylate, ethoxylated-o-phenylphenol acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,Examples of the (meth)acrylate compounds include 3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, lauryl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-dodecyl-1-hexadecanyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-[[(butylamino)carbonyl]oxy]ethyl (meth)acrylate, and 2-(2-ethoxyethoxy)ethyl (meth)acrylate. These other (meth)acrylate compounds may be used alone or in combination.

[0060] When the monomer composition in the first embodiment contains other (meth)acrylate compounds, the proportion of the other (meth)acrylate compounds in the monomer composition is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and even more preferably 30% by mass to 60% by mass. When the monomer composition in the first embodiment contains other (meth)acrylate compounds, the proportion of the urethane (meth)acrylate compound in the monomer composition is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and even more preferably 30% by mass to 60% by mass.

[0061] There are no particular limitations on the use of the monomer composition in the first embodiment, and the monomer composition in the first embodiment may be, for example, a monomer composition for use as a material for an appliance to be worn in the oral cavity, a monomer composition for use as a material for a medical device component, a monomer composition for use as a material for a denture base, or a monomer composition for use as a material for a surgical component.

[0062] [Photocurable composition] The photocurable composition of the first embodiment contains the urethane (meth)acrylate compound of the first embodiment and a polymerization initiator. The photocurable composition of the first embodiment may contain other components.

[0063] The photocurable composition in the first embodiment contains the urethane (meth)acrylate compound in the first embodiment, and therefore exhibits the effect of the urethane (meth)acrylate compound in the first embodiment (i.e., the effect of being suitable for imparting toughness to the cured product).

[0064] The photocurable composition in the first embodiment may be a composition containing the monomer composition in the first embodiment described above and a polymerization initiator.

[0065] The proportion of the urethane (meth)acrylate compound in the photocurable composition in the first embodiment may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, 80% by mass or more, or 90% by mass or more.

[0066] <Photopolymerization Initiator> The photocurable composition in the first embodiment contains at least one polymerization initiator. Examples of the polymerization initiator include general photopolymerization initiators used in the field of stereolithography. Examples of the photopolymerization initiator include alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, α-acyloxime ester compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, iron-phthalocyanine compounds, benzoin ether compounds, and anthraquinone compounds.

[0067] The photopolymerization initiator preferably contains at least one selected from the group consisting of alkylphenone compounds and acylphosphine oxide compounds. From the viewpoint of further improving the modeling accuracy of the stereolithography object, the photopolymerization initiator more preferably contains at least one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-hydroxy-cyclohexyl phenyl ketone, phenylglyoxylic acid methyl ester, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1,2-octanedione, and 1-{4-(phenylthio)-, 2-(O-benzoyloxime)}.

[0068] The amount of the polymerization initiator contained in the photocurable composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and even more preferably 1% by mass to 5% by mass, relative to the total amount of the photocurable composition.

[0069] <Rubber Particles> The photocurable composition of the first embodiment may contain rubber particles. The rubber particles function as an impact modifier. The urethane (meth)acrylate compound of the first embodiment contained in the photocurable composition of the first embodiment has excellent compatibility with the rubber particles. Therefore, the photocurable composition of the first embodiment containing rubber particles can produce a three-dimensional object with excellent toughness. For details about the rubber particles, reference may be made to the description of International Publication No. 2015 / 119163.

[0070] Examples of types of rubber particles include acrylic rubber particles, butadiene rubber particles, butadiene-acrylic rubber particles, butadiene-styrene rubber particles, methylmethacryl-butadiene-styrene rubber particles, and silicone rubber particles. The rubber particles may be selected in consideration of appropriate physical properties, but butadiene rubber particles and butadiene-acrylic rubber particles are preferred in consideration of the balance of various physical properties such as hardness and impact resistance. One type of rubber particle may be used, or two or more types of rubber particles may be used in combination.

[0071] Examples of rubber particles include rubber particles having a single layer structure and rubber particles having a multilayer structure. Rubber particles having a multilayer structure may have, for example, an inner layer made of a rubber-like polymer such as an acrylic (co)polymer, a butadiene (co)polymer, or a silicone polymer, and an outer layer made of a resin obtained by polymerizing a thermoplastic resin component around the inner layer. Furthermore, a rubber-like polymer in which a small amount of a crosslinkable polyfunctional monomer is copolymerized may also be used. The butadiene (co)polymer may be a butadiene-n-butyl acrylate copolymer, a butadiene-styrene copolymer, or the like. Resins obtained by polymerizing a thermoplastic resin component are preferably polymers with a glass transition temperature above room temperature. Note that the term "(co)polymer" refers to both homopolymers and copolymers.

[0072] For example, the acrylic rubber particles may be of a single layer structure made of a rubber-like polymer mainly composed of methyl methacrylate, or of a multilayer structure in which a thermoplastic resin layer mainly composed of methyl methacrylate is provided around an inner layer which is an elastic resin layer mainly composed of an acrylic acid alkyl ester such as n-butyl acrylate, or known acrylic rubber particles may be used.

[0073] The rubber particles are more preferably rubber particles obtained by graft polymerizing a thermoplastic resin component onto a rubber-like polymer having a crosslinked structure.

[0074] The thermoplastic resin component is not particularly limited as long as it is a monomer component that can be graft-polymerized with the rubber-like polymer, and examples thereof include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, N-substituted maleimide compounds, α,β-unsaturated carboxylic acid compounds, anhydrides thereof (e.g., maleic anhydride, etc.), etc. These monomer components may be used alone or in combination of two or more.

[0075] When the rubber-like polymer is an acrylic (co)polymer, it preferably contains one or more alkyl acrylate esters having an alkyl group containing 2 to 8 carbon atoms and one or more polyfunctional monomers. Furthermore, the acrylic (co)polymer may be a copolymer of a mixture containing a monomer copolymerizable with styrene, α-methylstyrene, vinyltoluene, or other styrene derivatives, acrylonitrile, methyl methacrylate, or the like, preferably styrene or a mixture of styrene and a styrene derivative. Examples of alkyl acrylate esters having an alkyl group containing 2 to 8 carbon atoms include ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, with n-butyl acrylate being more preferred. Examples of polyfunctional monomers include known acrylic polyfunctional monomers and polyvalent aromatic vinyl monomers (e.g., divinylbenzene).

[0076] The amounts of the components constituting the acrylic (co)polymer are not particularly limited, but a polymer composed of 50.0% to 99.9% by mass of an alkyl acrylate, 0.1% to 10% by mass of a polyfunctional monomer, and 0% to 49.9% by mass of a monomer copolymerizable therewith is preferred. Rubber particles obtained by graft polymerizing a thermoplastic resin component onto such an acrylic (co)polymer are commercially available, for example, as "Metablen (registered trademark) W-450" from Mitsubishi Rayon Co., Ltd.

[0077] When the rubber-like polymer is a butadiene-based (co)polymer, it is preferably a copolymer formed by reacting 5% by mass or more of 1,3-butadiene with less than 95% by mass of at least one monomer copolymerizable with 1,3-butadiene. Examples of monomers copolymerizable with 1,3-butadiene include styrene, acrylonitrile, and the aforementioned alkyl acrylate esters having 2 to 8 carbon atoms in the alkyl group. When the rubber-like polymer is a butadiene-based (co)polymer, a three-dimensional object produced from a photocurable composition containing rubber particles can be provided with high impact strength.

[0078] When copolymerizing 1,3-butadiene with a monomer copolymerizable with 1,3-butadiene, a polyfunctional monomer may be used in combination. Examples of the polyfunctional monomer include known acrylic polyfunctional monomers and polyvalent aromatic vinyl monomers (e.g., divinylbenzene).

[0079] From the viewpoint of forming a three-dimensional object having high impact strength, the butadiene-based (co)polymer is preferably a butadiene-n-butyl acrylate copolymer formed by reacting butadiene with n-butyl acrylate. Rubber particles obtained by graft polymerizing a thermoplastic resin component onto such a butadiene-based (co)polymer are commercially available, such as "MUX-60" from UMG ABS Co., Ltd., "Kane Ace (registered trademark) M-521" from Kaneka Corporation, and "Kane Ace (registered trademark) MZ-120" from Kaneka Corporation.

[0080] When the rubbery polymer is a silicone polymer, examples of the silicone polymer include room temperature curing silicone rubber, thermosetting silicone rubber, etc., and specific examples include dimethyl silicone rubber, vinyl methyl silicone rubber, methyl phenyl silicone rubber, fluorosilicone rubber, etc. Known silicone rubbers may also be used as the silicone polymer.

[0081] The average particle size of the rubber particles is preferably in the range of 0.03 μm to 2.0 μm. This allows the rubber particles to be suitably dispersed in the photocurable composition. Rubber particles of this size can be produced by emulsion polymerization.

[0082] The amount of rubber particles contained in the photocurable composition is preferably 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 30% by mass, more preferably 0.7% by mass to 25% by mass, and even more preferably 5% by mass to 20% by mass, relative to the total amount of the photocurable composition.

[0083] <Other Components> The photocurable composition of the first embodiment may contain other components in addition to the components described above, as necessary. Examples of other components include colorants, fillers, modifiers, stabilizers, antioxidants, solvents, etc. Furthermore, the photocurable composition of the first embodiment may contain, as other components, "other (meth)acrylate compounds other than the urethane (meth)acrylate compound of the first embodiment" as described above as components that may be contained in the monomer composition of the first embodiment. In this case, the proportions of the urethane (meth)acrylate compound of the first embodiment and the other (meth)acrylate compounds in the photocurable composition of the first embodiment are the same as the proportions of the urethane (meth)acrylate compound of the first embodiment and the other (meth)acrylate compounds in the monomer composition of the first embodiment when the other (meth)acrylate compounds are contained, respectively.

[0084] From the viewpoint of further improving the modeling accuracy of the photo-fabricated object, it is preferable that the photo-curable composition in the first aspect does not contain an inorganic filler (e.g., silica, barium borosilicate glass, etc.; the same applies below), or, if it contains an inorganic filler, the content of the inorganic filler relative to the total amount of the photo-fabricated curable composition is 10 mass % or less (more preferably 5 mass % or less, even more preferably 2 mass % or less, and even more preferably 1 mass % or less).

[0085] <Preferred Viscosity of Photocurable Composition> From the viewpoint of ease of handling of the photocurable composition, the photocurable composition in the first embodiment preferably has a viscosity measured with an E-type viscometer at 25°C and 50 rpm (hereinafter simply referred to as "viscosity") of 5 mPa s to 15,000 mPa s, where rpm means revolutions per minute.

[0086] <Stereolithography> The photocurable composition in the first embodiment is preferably a photocurable composition used for producing a three-dimensional object by stereolithography (hereinafter also referred to as a "stereolithography object"). The three-dimensional object in the first embodiment is a three-dimensional object made of the photocurable composition in the first embodiment (i.e., a three-dimensional object obtained by stereolithography of the photocurable composition in the first embodiment).

[0087] Examples of the stereolithography method include a liquid tank method (for example, a DLP method or an SLA method, preferably a DLP method), an inkjet method, and the like.

[0088] In liquid vat-type stereolithography, a portion of a photocurable composition for stereolithography (i.e., an uncured photocurable composition in a liquid state; the same applies below) contained in a liquid vat is cured by irradiating it with light to form a cured layer, and this process is repeated to stack cured layers, thereby obtaining a stereolithographic object. Liquid vat-type stereolithography differs from inkjet-type stereolithography, which uses inkjet nozzles, in that it uses a liquid vat. Liquid vat-type stereolithography is broadly divided into DLP (Digital Light Processing) stereolithography and SLA (Stereolithography) stereolithography. In the DLP method, planar light is irradiated onto the photocurable composition in the liquid vat. In the SLA method, laser light is scanned onto the photocurable composition in the liquid vat.

[0089] An example of DLP-based stereolithography uses a 3D printer (e.g., Kulzer's "Cara Print 4.0 pro," Asiga's "Max UV," etc.) equipped with: a build table movable in the vertical direction; a tray (i.e., a liquid tank) disposed below the build table (on the gravity side; the same applies below) that includes a light-transmitting portion and contains a photocurable composition; and a light source (e.g., an LED light source) disposed below the tray for irradiating the photocurable composition in the tray with planar light through the tray's light-transmitting portion. In this example, first, a gap of one layer is formed between the build table and the tray, and this gap is filled with photocurable composition. Next, planar light is irradiated from below through the tray's light-transmitting portion onto the photocurable composition filled in the gap, curing the irradiated area to form a first cured layer. Next, the gap between the build table and the tray is widened by the next layer, and the resulting space is filled with photocurable composition. Next, the photocurable composition that has filled the space is irradiated with light in the same manner as for curing the first layer to form a second cured layer. By repeating the above operation, cured layers are stacked to produce a three-dimensional object. In this example, the three-dimensional object may be further cured by further irradiating the produced three-dimensional object with light.

[0090] <Uses of Photocurable Composition> The use of the photocurable composition in the first embodiment is not particularly limited. The photocurable composition in the first embodiment is preferably a photocurable composition used for producing an instrument, a medical device component, a denture base, or a surgical component worn in the oral cavity. From the viewpoint of improving the toughness of a stereolithographic object, the photocurable composition in the first embodiment is more preferably a photocurable composition for producing the above-mentioned instrument, a medical device component, a denture base, or a surgical component worn in the oral cavity by stereolithography. Examples of medical devices used in the oral cavity include orthodontic retainers, night guards, sports mouth guards, bridges, implants, crowns, veneers, space maintainers, dental splints, dental inlays / onlays, dental attachments, dental resin bonding, and dental whitening trays. Examples of medical device components include dental models, artificial heart valves, artificial limbs, artificial hands, spinal fixation devices, catheters, stents, and osteoconduction implants. Denture bases include complete dentures, partial dentures, immediate dentures, overdentures, implant-supported dentures, flexible partial dentures, etc. Surgical components include artificial joints, external fixators, surgical guides, suction devices, plates and screws for fracture fixation, artificial joints, drain tubes, balloon catheters, stents, bioadhesives, intervertebral disc prostheses, etc.

[0091] [Medical device member, instrument used in oral cavity, denture base, and surgical member] The instrument used in oral cavity of the first aspect includes the three-dimensionally shaped object of the first aspect. The medical device member of the first aspect includes the three-dimensionally shaped object of the first aspect. The denture base of the first aspect includes the three-dimensionally shaped object of the first aspect. The surgical member of the first aspect includes the three-dimensionally shaped object of the first aspect. The instrument used in oral cavity of the first aspect, the medical device member of the first aspect, the denture base of the first aspect, and the surgical member of the first aspect all have excellent toughness.

[0092] [Method for manufacturing a stereolithographic object] The method for manufacturing a three-dimensional object in the first embodiment includes the steps of: generating the urethane (meth)acrylate compound in the first embodiment by the above-described manufacturing method X; preparing a photocurable composition containing the urethane (meth)acrylate compound in the first embodiment and a photopolymerization initiator; and obtaining a three-dimensional object from the photocurable composition. The method for manufacturing a three-dimensional object in the first embodiment may include other steps as necessary.

[0093] According to the method for manufacturing a three-dimensional object in the first aspect, a three-dimensional object having excellent toughness can be manufactured.

[0094] For the step of producing a urethane (meth)acrylate compound, the above-mentioned Production Method X can be referred to. For the step of preparing a photocurable composition, at least a urethane (meth)acrylate compound and a photopolymerization initiator may be mixed by a known method. For the step of obtaining a three-dimensional object, the above-mentioned known stereolithography technology can be applied.

[0095] Second Aspect A second aspect of the present disclosure will be described below.

[0096] [Photocurable composition] The photocurable composition of the second embodiment contains a urethane (meth)acrylate compound represented by the following formula (1) and a photopolymerization initiator. The photocurable composition of the second embodiment can provide a cured product with excellent flexural strength. In the photocurable composition of the second embodiment, the urethane (meth)acrylate compound represented by the following formula (1) serves as a polymerizable monomer (hereinafter also simply referred to as "monomer"). When the photocurable composition of the second embodiment is irradiated with light, the action of the photopolymerization initiator initiates polymerization of the urethane (meth)acrylate compound represented by formula (1) as the monomer. As this polymerization progresses, a cured product is obtained. In the photocurable composition of the second embodiment, the flexural strength of the resulting cured product is improved by using a urethane (meth)acrylate compound having a specific structure represented by the following formula (1) as the monomer.

[0097] The urethane (meth)acrylate compound represented by formula (1) in the second embodiment is the same compound as the urethane (meth)acrylate compound represented by formula (1) in the first embodiment.

[0098] <Urethane (meth)acrylate compound represented by formula (1)> The photocurable composition in the second embodiment contains at least one urethane (meth)acrylate compound represented by the following formula (1).

[0099]

[0100] In formula (1), two R １ are each independently a divalent organic group, n Xs are each independently a divalent group represented by formula (X1), (n+1) Ys are each independently a divalent group represented by formula (Y1) or formula (Y2), and two R ２ are each independently a hydrogen atom or a methyl group, and n is an integer of 1 to 10. In formula (X1), R ＸＡ is a divalent hydrocarbon group containing a cyclic structure, and (m+k) R ＸＢ are each independently a divalent hydrocarbon group, m and k are each independently an integer of 1 to 5, and two *'s each indicate a bonding position. Ｙ１Ａ are each independently a linear alkylene group having 1 to 5 carbon atoms or a methylmethylene group, and R Ｙ１Ｂ is a divalent cyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position. Ｙ２Ａ is a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position.

[0101] The urethane (meth)acrylate compound according to the second aspect is suitable for obtaining a three-dimensionally shaped object having excellent toughness. Specifically, a three-dimensionally shaped object (e.g., a stereolithography object) produced using the urethane (meth)acrylate compound according to the second aspect exhibits excellent toughness compared to a three-dimensionally shaped object produced using conventional UDMA. The effect of improving the toughness of the three-dimensionally shaped object is believed to be due to the structure of formula (1) above, which includes a urethane bond (—NH(C═O)O— bond), X containing a cyclic structure, and Y containing a cyclic structure. Furthermore, a three-dimensionally shaped object (e.g., a stereolithography object) produced using the urethane (meth)acrylate compound according to the second aspect exhibits a flexural modulus equivalent to that of a three-dimensionally shaped object produced using conventional UDMA.

[0102] In formula (1), two R １ are each independently a divalent organic group. １ is preferably a divalent hydrocarbon group, more preferably an alkylene group. １ The number of carbon atoms in the divalent hydrocarbon group represented by the formula (1) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. ２ are each independently a hydrogen atom or a methyl group.

[0103] The moieties at both ends of the urethane (meth)acrylate compound represented by formula (1) are groups represented by the following formula (1E): The groups represented by the following formula (1E) (i.e., the moieties at both ends in formula (1)) can be formed using a hydroxy group-containing (meth)acrylate compound (specifically, a compound represented by the following formula (1EM)) for forming the moieties at both ends in formula (1).

[0104]

[0105] R in formula (1E) and formula (1EM) １ and R ２ are R in formula (1), respectively. １ and R ２ is synonymous with.

[0106] In formula (1), n ​​X's are each independently a divalent group represented by formula (X1). ＸＡ is a divalent hydrocarbon group containing a cyclic structure, and (m+k) R ＸＢ are each independently a divalent hydrocarbon group, m and k are each independently an integer of 1 to 5, and two * symbols each indicate a bonding position.

[0107] In formula (X1), R ＸＡ The divalent hydrocarbon group having a cyclic structure represented by the formula (X1-1) is preferably an arylene group having 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms) or an arylene alkylene arylene group having 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms), more preferably an arylene alkylene arylene group having 6 to 30 carbon atoms (more preferably 6 to 20 carbon atoms), and even more preferably a divalent hydrocarbon group represented by either of the following formula (X1-1) or (X1-2) (* indicates a bonding position).

[0108]

[0109] In formula (X1), R ＸＢ The divalent hydrocarbon group represented by the formula (I) is preferably a linear or branched alkylene group, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms), and even more preferably an ethylene group or a methylethylene group.

[0110] X in formula (1) (i.e., the divalent group represented by formula (X1)) can be formed using a diol compound for forming X in formula (1) (more specifically, a compound in which a hydroxy group is bonded to each of the two * positions in the divalent group represented by formula (X1)). Examples of diol compounds for forming X in formula (1) include: bisphenol A-propylene oxide 2-4 mol adduct, bisphenol A-propylene oxide 2-5 mol adduct, bisphenol A-propylene oxide 2-9 mol adduct, bisphenol F-propylene oxide 2-5 mol adduct, and the like.

[0111] In formula (1), (n+1) Ys are each independently a divalent group represented by formula (Y1) or formula (Y2).

[0112] In formula (Y1), two R Ｙ１Ａ are each independently a linear alkylene group having 1 to 5 carbon atoms or a methylmethylene group, and R Ｙ１Ｂ is a divalent cyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position.

[0113] In formula (Y1), R Ｙ１Ｂ The divalent cyclic hydrocarbon group having 5 to 12 carbon atoms represented by the formula (Y1B-1) is preferably a divalent group represented by any one of the following formulae (Y1B-1) to (Y1B-6).

[0114]

[0115] In each of formulae (Y1B-1) to (Y1B-6), two * indicate the bonding position.

[0116] In formula (Y1), R Ｙ１Ａ are preferably each independently a methylene group or a methylmethylene group.

[0117] The divalent group represented by formula (Y1) is preferably a divalent group represented by any one of the following formulae (Y1-1) to (Y1-7).

[0118]

[0119] In each of formulas (Y1-1) to (Y1-7), two * each indicate a bonding position.

[0120] In formula (Y2), R Ｙ２Ａ The divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms represented by the formula (Y2A-1) is preferably a divalent group represented by any one of the following formulae (Y2A-1) to (Y2A-6).

[0121]

[0122] Y in formula (1) (i.e., a divalent group represented by either formula (Y1) or formula (Y2)) can be formed using a diisocyanate compound corresponding to Y in formula (1) (specifically, a compound in which an isocyanate group is bonded to each of the two * positions in the divalent group represented by either formula (Y1) or formula (Y2)).

[0123] The molecular weight of the urethane (meth)acrylate compound represented by formula (1) is not particularly limited, but is preferably not more than 24,000, more preferably not more than 12,000, and more preferably not more than 8,000. The lower limit of the molecular weight of the urethane (meth)acrylate compound represented by formula (1) is not particularly limited as long as formula (1) is satisfied, but examples of the lower limit of the molecular weight include 600 and 800.

[0124] Specific examples (monomers 1 to 9) of the urethane (meth)acrylate compound represented by formula (1) are shown below, but the urethane (meth)acrylate compound represented by formula (1) is not limited to the following specific examples. Note that the following monomer 2 is monomer A in the examples described later.

[0125]

[0126]

[0127] The content of the urethane (meth)acrylate compound represented by formula (1) in the photocurable composition of the second embodiment is preferably 5% by mass or more, more preferably 5% by mass to 80% by mass, more preferably 5% by mass to 50% by mass, and even more preferably 5% by mass to 40% by mass.

[0128] In the photocurable composition of the second embodiment, the proportion of the urethane (meth)acrylate compound represented by formula (1) in the total amount of monomers contained therein is preferably 30% by mass or more, more preferably 40% by mass or more, and may be 100% by mass or less.

[0129] (Example of a method for producing a urethane (meth)acrylate compound represented by formula (1) (Production method X)) Hereinafter, an example of a production method for producing a urethane (meth)acrylate compound represented by formula (1) (hereinafter also referred to as "Production method X") will be described.

[0130] Production method X includes a step of reacting the above-mentioned "hydroxy group-containing (meth)acrylate compound for forming both terminal moieties in formula (1)", the above-mentioned "diol compound for forming X in formula (1)", and the above-mentioned "diisocyanate compound corresponding to Y in formula (1)", to produce a urethane (meth)acrylate compound represented by formula (1), which is a reaction product of these compounds (hereinafter also referred to as "raw materials"). Production method X may include other steps as necessary.

[0131] The reaction in Production Method X may be carried out in a solvent or without a solvent. Any known solvent can be used as long as it is inert to the reaction. Examples of the solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and perclene; and polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, dimethyl sulfoxide, and sulfolane. These solvents may be used alone or in combination.

[0132] - Catalyst - A catalyst may be used in the above reaction in Production Method X. Examples of the catalyst include: organotin compounds such as dibutyltin dilaurate (also known as dibutyltin dilaurate), dibutyltin dioctate, and tin octoate; organometallic compounds other than tin compounds such as copper naphthenate, cobalt naphthenate, zinc naphthenate, zirconium acetylacetonate, iron acetylacetonate, and germanium acetylacetonate; amine compounds such as triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undecene, N,N-dimethylcyclohexylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-pentamethyldiethylenetriamine, N,N,N',N'-tetra(3-dimethylaminopropyl)-methanediamine, N,N'-dimethylpiperazine, and 1,2-dimethylimidazole, and salts thereof; trialkylphosphine compounds such as tri-n-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine, and tri-n-octylphosphine; and the like. Of these, dibutyltin dilaurate and tin octoate are preferred.

[0133] The amount of the catalyst used may be 0.001% by mass to 1.0% by mass, or may be 0.01% by mass to 0.5% by mass, based on the total of the aforementioned "hydroxy group-containing (meth)acrylate compound for forming both terminal moieties in formula (1)", the aforementioned "diol compound for forming X in formula (1)", and the aforementioned "diisocyanate compound corresponding to Y in formula (1)".

[0134] The reaction temperature is not particularly limited and is, for example, 20°C to 170°C, preferably 30°C to 140°C, and more preferably 50°C to 120°C.

[0135] The reaction time is not particularly limited as it depends on conditions such as the reaction temperature, and is, for example, 5 minutes to 50 hours. The end point of the reaction can be confirmed by analysis by HPLC (high performance liquid chromatography), etc.

[0136] A polymerization inhibitor may be used during the above reaction in Production Method X. Examples of the polymerization inhibitor include dibutylhydroxytoluene (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), and phenothiazine (PTZ).

[0137] The amount of the polymerization inhibitor used may be 0.001% by mass to 0.5% by mass, 0.002% by mass to 0.3% by mass, or 0.005% by mass to 0.3% by mass, based on the total of the aforementioned "hydroxy group-containing (meth)acrylate compound for forming both terminal moieties in formula (1)", the aforementioned "diol compound for forming X in formula (1)", and the aforementioned "diisocyanate compound corresponding to Y in formula (1)".

[0138] <Photopolymerization initiator> The photocurable composition of the second embodiment contains at least one photopolymerization initiator. As the photopolymerization initiator, for example, a general photopolymerization initiator used in the dental field can be used.

[0139] The photopolymerization initiator is not particularly limited, and examples thereof include α-diketone / reducing agent, ketal / reducing agent, thioxanthone / reducing agent, α-diketone / organic peroxide / reducing agent, etc. Examples of α-diketones include camphorquinone, etc. Examples of ketals include benzyl dimethyl ketal, etc. Examples of thioxanthones include 2-chlorothioxanthone, etc.

[0140] Examples of the reducing agent include tertiary amines. Examples of the tertiary amines include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-i-propylaniline, N,N-dimethyl-4-t-butylaniline, and N,N-dimethyl-3,5-di-t-butylaniline. aniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-i-propylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-di(2-hydroxyethyl) )-3,5-di-i-propylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, ethyl 4-dimethylaminobenzoate, 2-butoxyethyl 4-dimethylaminobenzoate, (2-methacryloyloxy)ethyl 4-dimethylaminobenzoate, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, (2-dimethylamino)ethyl methacrylate, N,N-bis(methacryloyloxyethyl)-N-methylamine, N,N-bis(methacryloyloxyethyl)-N-ethylamine, N,N-bis(2-hydroxyethyl)-N-methacryloyloxyethylamine, N,N-bis(methacryloyloxyethyl)-N-(2-hydroxyethyl)amine, tris(methacryloyloxyethyl)amine, and the like.

[0141] Further, examples of the reducing agent include aldehydes (such as citronellal) and compounds having a thiol group (such as 2-mercaptobenzoxazole).

[0142] Examples of photopolymerization initiators for photopolymerization by ultraviolet irradiation include benzoin alkyl ether, benzil dimethyl ketal, and (bis)acylphosphine oxides.

[0143] Examples of (bis)acylphosphine oxides include acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.) and bisacylphosphine oxides (bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, etc.). These (bis)acylphosphine oxide photopolymerization initiators may be used alone or in combination with reducing agents such as various amines, aldehydes, mercaptans, and sulfinates. These (bis)acylphosphine oxide photopolymerization initiators may also be used in combination with the above-mentioned visible light photopolymerization initiators.

[0144] The photopolymerization initiator may be used by referring to, for example, International Publication No. 2021 / 29406, International Publication No. 2019 / 107323, International Publication No. 2020 / 040141, etc.

[0145] In the second embodiment, the proportion of the photopolymerization initiator relative to the total amount of the photocurable composition is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 10% by mass, and even more preferably 0.1% by mass to 5% by mass.

[0146] <Filler> The curable composition in the second embodiment may contain at least one filler. A typical filler used in the dental field can be used as the filler. Fillers are generally broadly classified into organic fillers and inorganic fillers. Examples of organic fillers include fine powders of polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, and the like.

[0147] Examples of inorganic fillers include fine powders of various glasses (mainly composed of silicon dioxide and optionally containing oxides of heavy metals, boron, aluminum, etc.), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite, etc. Specific examples of such inorganic fillers include barium borosilicate glass, strontium boroaluminosilicate glass, lanthanum glass, fluoroaluminosilicate glass, boroaluminosilicate glass, etc.

[0148] The filler may be used by referring to, for example, International Publication No. 2021 / 29406, International Publication No. 2019 / 107323, International Publication No. 2020 / 040141, etc.

[0149] When the photocurable composition of the second embodiment contains a filler, the content of the filler is preferably 90% by mass or less, more preferably 5% by mass to 90% by mass, even more preferably 10% by mass to 90% by mass, still more preferably 20% by mass to 90% by mass, and preferably 40% by mass to 90% by mass, relative to the total amount of the photocurable composition.

[0150] <Other Monomers> The photocurable composition of the second embodiment may contain other monomers in addition to the urethane (meth)acrylate compound represented by formula (1).

[0151] For example, the photocurable composition in the second aspect may include a urethane(meth)acrylate compound represented by formula (1) as a monomer for improving the strength of the resulting cured product (hereinafter also referred to as the "main monomer"), and a monomer for reducing the viscosity of the photocurable composition to improve its operability (hereinafter also referred to as the "diluting monomer"). In this case, the main monomer may include a urethane(meth)acrylate compound represented by formula (1), and a monomer other than the urethane(meth)acrylate compound represented by formula (1). Examples of the monomer other than the urethane(meth)acrylate compound represented by formula (1) as the main monomer include a urethane(meth)acrylate compound other than the urethane(meth)acrylate compound represented by formula (1) (for example, monomer B in the examples described later), a (meth)acrylate compound having a cyclic structure and not containing a urethane bond, and the like.

[0152] Examples of urethane (meth)acrylate compounds other than the urethane (meth)acrylate compound represented by formula (1) include: a compound in which n in formula (1) is changed to 0 (for example, Monomer B in the Examples described later); and a compound that does not contain a cyclic structure and contains a urethane bond and two (meth)acryloyl groups (for example, UDMA (i.e., 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate)).

[0153] Examples of (meth)acrylate compounds containing a cyclic structure but not a urethane bond include 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, benzyl (meth)acrylate, m-phenoxybenzyl acrylate, ethoxylated-o-phenylphenol acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol. (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, and the like.

[0154] Examples of the diluent monomer include (meth)acrylate compounds that do not contain a cyclic structure or a urethane bond. Examples of the (meth)acrylate compounds that do not contain a cyclic structure or a urethane bond include neopentyl di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol. di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, lauryl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-dodecyl-1-hexadecanyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-[[(butylamino)carbonyl]oxy]ethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, and the like.

[0155] When the photocurable composition in the second aspect contains a main monomer including a urethane (meth)acrylate compound represented by formula (1) and a diluent monomer, the proportion of the main monomer in the total amount of monomers contained in the photocurable composition is preferably 40% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and even more preferably 60% by mass to 80% by mass.

[0156] When the photocurable composition in the second aspect contains a main monomer including a urethane (meth)acrylate compound represented by formula (1) and a diluent monomer, the proportion of the diluent monomer in the total amount of monomers contained in the photocurable composition is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass.

[0157] The proportion of the urethane (meth)acrylate compound represented by formula (1) in the total amount of main monomers is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, and may be 100% by mass or less.

[0158] The content of all monomers in the photocurable composition in the second embodiment is preferably 10% by mass or more, more preferably 10% by mass to 95% by mass, even more preferably 10% by mass to 90% by mass, still more preferably 10% by mass to 80% by mass, and preferably 10% by mass to 60% by mass, relative to the total amount of the photocurable composition.

[0159] <Other Components> The photocurable composition of the second embodiment may contain other components in addition to the components described above, as necessary. Examples of other components include polymerization inhibitors, colorants (e.g., pigments, dyes, etc.), reinforcing materials (e.g., fibers, etc.), bactericides, disinfectants, stabilizers, preservatives, etc.

[0160] <Preferred Viscosity of Photocurable Composition> From the viewpoint of ease of handling of the photocurable composition, the photocurable composition in the second embodiment preferably has a viscosity measured with an E-type viscometer at 50 rpm and 80°C (hereinafter also simply referred to as "viscosity") of 10 mPa s to 50,000 mPa s, where rpm means revolutions per minute.

[0161] <Preferred Uses of the Photocurable Composition> There are no particular limitations on the uses of the photocurable composition of the second embodiment. The photocurable composition of the second embodiment is particularly suitable as a photocurable composition for dental materials because it can produce a cured product with excellent bending strength. Examples of dental materials will be described later.

[0162] [Cured Product] The cured product in the second embodiment is a cured product of the photocurable composition in the second embodiment described above (i.e., a cured product obtained by curing the photocurable composition in the second embodiment). Curing of the photocurable composition in the second embodiment to obtain the cured product in the second embodiment can be carried out by irradiating the photocurable composition in the second embodiment with light to polymerize the urethane (meth)acrylate compound represented by formula (1) as a monomer (and other monomers, if contained).

[0163] The photocurable composition of the second embodiment can be cured under appropriate conditions using a photopolymerization initiator polymerization method. For example, when a photopolymerization initiator for visible light irradiation is contained, the photocurable composition can be processed into a predetermined shape and then irradiated with visible light for a predetermined time using a known light irradiation device to obtain a desired cured product. Conditions such as irradiation intensity can be appropriately changed depending on the curability of the photocurable composition. In addition, the cured product cured by light irradiation, including visible light, may be further heat-treated under appropriate conditions to improve the mechanical properties of the cured product.

[0164] [Dental Material] The dental material of the second aspect comprises the photocurable composition of the second aspect or a cured product of the photocurable composition of the second aspect. The dental material of the second aspect comprising the photocurable composition of the second aspect is, for example, a composite resin for filling caries cavities. In this case, the objective can be achieved by filling a cavity in the oral cavity with the composite resin for filling caries cavities and then photocuring it using a known light irradiation device. The dental material of the second aspect comprising the photocurable composition of the second aspect may also be a composite resin for crowns. In this case, the composite resin for crowns can be processed into an appropriate shape, photocured using a known light irradiation device, and then heat-treated under specified conditions to obtain the desired dental crown material.

[0165] The photocurable composition of the second aspect may be used in dental treatment. A dental treatment method using the photocurable composition of the second aspect (or a dental material containing this photocurable composition) may include a step of polymerizing the photocurable composition of the second aspect in the oral cavity to obtain a cured product. The photocurable composition of the second aspect (or a dental material containing this photocurable composition) when used to obtain a cured product in the oral cavity by polymerization is suitable as, for example, a dental adhesive resin cement, a composite resin for filling and restoring, etc.

[0166] A dental treatment method using the photocurable composition of the second aspect (or a dental material containing this photocurable composition) may include a step of polymerizing the photocurable composition of the second aspect extraorally to obtain a cured product, and a step of applying the cured product intraorally. The step of polymerizing the photocurable composition of the second aspect extraorally to obtain a cured product may be a step of polymerizing the photocurable composition of the second aspect in a casting mold to obtain a cured product. The cured product obtained by polymerizing the photocurable composition of the second aspect extraorally may be processed as necessary, and the processed cured product may be applied intraorally. The cured product obtained by polymerizing the photocurable composition of the second aspect extraorally (or a dental material containing this cured product) is suitable for use as, for example, a resin block for CAD / CAM, a temporary crown, an artificial tooth, etc.

[0167] The photocurable composition and dental material of the second aspect can be preferably used as, for example, a dental restorative material, a denture base resin, a denture base lining material, an impression material, a luting material (e.g., resin cement, resin-added glass ionomer cement), a dental adhesive (e.g., orthodontic adhesive, cavity application adhesive), a fissure sealant, a resin block for CAD / CAM, a temporary crown, an artificial tooth material, etc. Dental restorative materials can be classified by application range into composite resins for crowns, composite resins for filling caries cavities, composite resins for core construction, composite resins for filling and restoring, etc. Of these, the photocurable composition and dental material of the second aspect are particularly suitable for dental restorative materials such as composite resins.

[0168] Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples. Hereinafter, the term "monomer" simply means a (meth)acrylate compound unless otherwise specified.

[0169] First, an example of the first aspect will be described below.

[0170] The abbreviations of the compounds used in the production of the urethane (meth)acrylate compounds (monomers 1 to 9) represented by formula (1) are shown below. <Diol compounds corresponding to X in formula (1)> NEWPOL BP-23P (hereinafter also referred to as "BP23P"): bisphenol A-propylene oxide 2-4 mol adduct, manufactured by Sanyo Chemical Industries, Ltd. NEWPOL BP-3P (hereinafter also referred to as "BP3P"): bisphenol A-propylene oxide 2-5 mol adduct, manufactured by Sanyo Chemical Industries, Ltd. NEWPOL BP-5P (hereinafter also referred to as "BP5P"): bisphenol A-propylene oxide 2-9 mol adduct, manufactured by Sanyo Chemical Industries, Ltd. BPF2P: bisphenol F-propylene oxide 2-5 mol adduct, manufactured by Mitsui Chemicals, Inc. <Hydroxy group-containing (meth)acrylate compounds corresponding to the terminal moiety in formula (1)> HEA: 2-hydroxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. HEMA: 2-hydroxyethyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd. 4-HBA: 4-Hydroxybutyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. <Diisocyanate compounds corresponding to Y in formula (1)> XDI...m-xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc. NBDI...norbornane-2,6-diylbis(methylene)diisocyanate, manufactured by Mitsui Chemicals, Inc. 1,3-H6XDI...1,3-bis(isocyanatomethyl)cyclohexane, manufactured by Tokyo Chemical Industry Co., Ltd. 1,4-H6XDI...1,4-bis(isocyanatomethyl)cyclohexane, manufactured by Mitsui Chemicals, Inc. <Polymerization catalyst> DBTDL...dibutyltin dilaurate, manufactured by Tokyo Chemical Industry Co., Ltd. <Polymerization inhibitor> BHT...2,6-di-tert-butyl-p-cresol, manufactured by Tokyo Chemical Industry Co., Ltd.

[0171] The components used in preparing the photocurable composition are shown below: <(Meth)acrylate compound represented by formula (1)> Monomers 1 to 9...Monomers 1 to 9 described below. Raw materials for producing each monomer are shown in Table 2. <Other Monomers> Genomer 4297... 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA) (manufactured by Rahn AG) BZMA... benzyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc.) THFMA... tetrahydrofurfuryl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) CTFA... cyclic trimethylolpropane formal acrylate (manufactured by Osaka Organic Chemical Industry Ltd.) (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) <Photopolymerization Initiator> Omnirad 819... phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, IGM Resins B.V. <Rubber particles> Kane Ace (registered trademark) MZ-120... buta-1,3-diene butyl acrylate methyl methacrylate polymer, manufactured by Kaneka Corporation Kane Ace (registered trademark) M-511... buta-1,3-diene methyl methacrylate styrene polymer, manufactured by Kaneka Corporation Kane Ace (registered trademark) M-721... buta-1,3-diene methyl methacrylate styrene polymer, manufactured by Kaneka Corporation Kane Ace (registered trademark) B-513... buta-1,3-diene methyl methacrylate styrene polymer, manufactured by Kaneka Corporation

[0172] <Production of (meth)acrylate compounds represented by formula (1) (monomers 1 to 9)> As specific examples of the (meth)acrylate compounds represented by formula (1) in the present disclosure, monomers 1 to 9 were produced. Detailed procedures for producing each of the monomers 1 to 9 will be described later.

[0173] (Liquid Chromatography Mass Spectrometry (LC-MS) Conditions) In the production of each of Monomers 1 to 9, LC-MS was performed using the following equipment and analytical conditions. LC-MS: ACQUITY UPLC H CLASS (manufactured by Waters Corporation) Column: ACQUITY UPLC BEH C18 1.7 μm 2.1×100 mm (manufactured by Waters Corporation) Flow rate: 0.5 ml / min Detection wavelength: 210 nm Mass spectrometry: electrospray spectrometry (ESI) Mobile phase: mobile phase shown in Table 1 below

[0174]

[0175] (Production of Monomer 1) Newpol BP-3P (100 g) and 1,3-H6XDI (85.90 g, 0.44 mol) were placed in a 0.5-liter four-neck flask (hereinafter also referred to as the "reactor") equipped with a thoroughly dried stirring blade and a thermometer, and the mixture was heated to 50°C and stirred. Subsequently, DBTDL (0.18 g, 0.29 mmol) was added as a polymerization catalyst. After the addition of DBTDL, the mixture was cooled so that the reaction temperature was 50 to 80°C, and then heated to 90°C. After the reaction was carried out for 3 hours, BHT (0.48 g, 2.18 mmol) was added as a polymerization inhibitor, and the mixture was stirred until homogeneous. Thereafter, HEMA (52.44 g, 0.40 mol) was added dropwise over 30 minutes, and the reaction was carried out at 90°C for 4 hours. During this time, the progress of the reaction was monitored by liquid chromatography-mass spectrometry (LC-MS), and the end point of the reaction was confirmed. Specifically, LC-MS confirmed a decrease in the peak of Newpol BP-3P, and an increase in a new peak of Monomer 1 below, which is a specific example of the (meth)acrylate compound represented by formula (1). Specifically, LC-MS confirmed that the peak of Monomer 1 was detected between retention times of 15.5 and 25.0 minutes, the (peak area of ​​Monomer 1 / peak area of ​​HEMA) was 21.7, the mass of Monomer 1 was detected from 993 to 2781 as [M+H], and it was confirmed that x+y was 2 to 5 and n was 1 to 4. The product was discharged from the reactor, yielding 238 g of Monomer 1.

[0176]

[0177] (Production of Monomer 2) Monomer 2, a specific example of a (meth)acrylate compound represented by formula (1), was produced in the same manner as in the production of Monomer 1, except that 1,3-H6XDI was replaced with the same molar amount of XDI. LC-MS confirmed a decrease in the peak of Newpol BP-3P and an increase in a new peak of Monomer 2. Specifically, in LC-MS, the peak of Monomer 2 was detected between retention times of 14.0 and 24.0 minutes, the (peak area of ​​Monomer 2 / peak area of ​​HEMA) was 26.8, the mass of Monomer 2 was detected from 981 to 2751 as [M+H], and it was confirmed that x+y was 2 to 5 and n was 1 to 4. The product was discharged from the reactor, yielding 235 g of Monomer 2.

[0178]

[0179] (Production of Monomer 3) Monomer 3, a specific example of a (meth)acrylate compound represented by formula (1), was produced in the same manner as in the production of Monomer 1, except that 1,3-H6XDI was replaced with the same mole number of NBDI. LC-MS confirmed a decrease in the peak of Newpol BP-3P and an increase in a new peak of Monomer 3. Specifically, in LC-MS, the peak of Monomer 3 was detected between retention times of 14.0 and 24.0 minutes, the (peak area of ​​Monomer 3 / peak area of ​​HEMA) was 10.8, and the mass of Monomer 3 was detected from 1017 to 2841 as [M+H], confirming that x+y was 2 to 5 and n was 1 to 4. 243 g of Oligomer 3 was obtained by discharging the product from the reactor.

[0180]

[0181] (Production of Monomer 4) Monomer 4, a specific example of a (meth)acrylate compound represented by formula (1), was produced in the same manner as in the production of Monomer 1, except that 1,3-H6XDI was replaced with the same number of moles of 1,4-H6XDI. LC-MS confirmed a decrease in the peak of Newpol BP-3P and an increase in a new peak of Monomer 4. Specifically, in LC-MS, the peak of Monomer 4 was detected between retention times of 15.5 and 25.0 minutes, the (peak area of ​​Monomer 4 / peak area of ​​HEMA) was 17.5, and the mass of Monomer 4 was detected from 993 to 2781 as [M+H], confirming that x+y was 2 to 5 and n was 1 to 4. 238 g of Monomer 4 was obtained by discharging the product from the reactor.

[0182]

[0183] (Production of Monomer 5) Monomer 5, a specific example of the (meth)acrylate compound represented by formula (1), was produced in the same manner as in the production of Monomer 2, except that HEMA was replaced with the same moles of HEA. LC-MS confirmed a decrease in the peak of Newpol BP-3P, and an increase in a new peak of Monomer 5. Specifically, in LC-MS, the peak of Monomer 5 was detected between retention times of 14.0 and 24.0 minutes, the (peak area of ​​Monomer 5 / peak area of ​​HEA) was 15.7, the mass of Monomer 5 was detected from 953 to 2723 as [M+H], and it was confirmed that x+y was 2 to 5 and n was 1 to 4. The product was discharged from the reactor, yielding 230 g of Oligomer 5.

[0184]

[0185] (Production of Monomer 6) Monomer 6, a specific example of a (meth)acrylate compound represented by formula (1), was produced in the same manner as in the production of Monomer 2, except that HEMA was replaced with the same moles of 4-HBA. LC-MS confirmed a decrease in the peak of Newpol BP-3P and an increase in a new peak of Monomer 6. Specifically, in LC-MS, the peak of Monomer 6 was detected between retention times of 15.5 and 24.0 minutes, the (peak area of ​​Monomer 6 / peak area of ​​4-HBA) was 22.8, the mass of Monomer 6 was detected from 1009 to 2779 as [M+H], and it was confirmed that x+y was 2 to 5 and n was 1 to 4. The product was discharged from the reactor, yielding 241 g of Oligomer 6.

[0186]

[0187] (Production of Monomer 7) Newpol BP-23P (100 g) and XDI (98.34 g, 0.52 mol) were placed in a 0.5-liter four-neck flask (hereinafter also referred to as the "reactor") equipped with a thoroughly dried stirring blade and a thermometer, and the mixture was heated to 50°C and stirred. Subsequently, DBTDL (0.19 g, 0.31 mmol) was added. After the addition of DBTDL, the mixture was cooled so that the reaction temperature was 50-80°C, and then heated to 90°C. After the reaction was carried out for 3 hours, BHT (0.52 g, 2.36 mmol) was added and the mixture was stirred until a homogeneous mixture was obtained. Then, HEMA (61.96 g, 0.47 mol) was added dropwise over 30 minutes, and the reaction was carried out at 90°C for 4 hours. During this time, the progress of the reaction was monitored by liquid chromatography-mass spectrometry (LC-MS), and the end point of the reaction was confirmed. Specifically, LC-MS confirmed a decrease in the peak of Newpol BP-23P, and an increase in a new peak of Monomer 7 below, which is a specific example of the (meth)acrylate compound represented by Formula (1). Specifically, LC-MS confirmed that the peak of Monomer 7 was detected between retention times of 13.5 minutes and 24.0 minutes, the (peak area of ​​Monomer 7 / peak area of ​​HEMA) was 8.8, the mass of Monomer 7 was detected from 981 to 2693 as [M+H], and it was confirmed that x+y was 2 to 4 and n was 1 to 4. The product was discharged from the reactor, yielding 260 g of Monomer 7.

[0188]

[0189] (Production of Monomer 8) Newpol BP-5P (100 g) and XDI (63.43 g, 0.33 mol) were placed in a 0.5-liter four-neck flask (hereinafter also referred to as the "reactor") equipped with a thoroughly dried stirring blade and thermometer, and the temperature was raised to 50°C and stirring was continued. Subsequently, DBTDL (0.20 g, 0.32 mmol) was added. After the addition of DBTDL, the reaction temperature was cooled to 50-80°C and then raised to 90°C. After the reaction was carried out for 3 hours, BHT (0.44 g, 2.03 mmol) was added and the mixture was stirred until homogeneous. Then, HEMA (39.97 g, 0.30 mol) was added dropwise over 30 minutes, and the reaction was carried out at 90°C for 4 hours. The progress of the reaction was monitored by liquid chromatography-mass spectrometry (LC-MS), and the end point of the reaction was confirmed. Specifically, LC-MS confirmed a decrease in the peak of Newpol BP-5P, and an increase in a new peak of Monomer 8 below, which is a specific example of the (meth)acrylate compound represented by Formula (1). Specifically, LC-MS confirmed that the peak of Monomer 8 was detected between retention times of 14.0 and 24.0 minutes, the (peak area of ​​Monomer 8 / peak area of ​​HEMA) was 5.8, and the mass of Monomer 8 was detected from 981 to 2983 as [M+H], confirming that x+y was 2 to 9 and n was 1 to 4. The product was discharged from the reactor, yielding 203 g of Monomer 8.

[0190]

[0191] (Production of Monomer 9) BPF2P (100 g) and XDI (103.59, 0.55 mol) were placed in a 0.5-liter four-neck flask (hereinafter also referred to as the "reactor") equipped with a thoroughly dried stirring blade and thermometer, and the temperature was raised to 50°C and stirring was continued. Subsequently, DBTDL (0.20 g, 0.32 mmol) was added. After the addition of DBTDL, the reaction temperature was cooled to 50-80°C and then raised to 90°C. After the reaction was carried out for 3 hours, BHT (0.53 g, 2.44 mmol) was added and the mixture was stirred until homogeneous. Thereafter, HEMA (65.27 g, 0.50 mol) was added dropwise over 30 minutes, and the reaction was carried out at 90°C for 4 hours. During this time, the progress of the reaction was monitored by liquid chromatography-mass spectrometry (LC-MS), and the end point of the reaction was confirmed. Specifically, LC-MS confirmed a decrease in the peak of BPF2P, and an increase in a new peak of Monomer 9 below, which is a specific example of the (meth)acrylate compound represented by Formula (1). Specifically, LC-MS confirmed that the peak of Monomer 9 was detected between retention times of 14.0 minutes and 24.0 minutes, the (peak area of ​​Monomer 9 / peak area of ​​HEMA) was 29.3, the mass of Monomer 9 was detected as [M+H] from 953 to 2639, and it was confirmed that x+y was 2 to 5 and n was 1 to 4. The product was discharged from the reactor, yielding 268 g of Monomer 9.

[0192]

[0193] Examples 1 to 16, Comparative Example 1 Preparation of Photocurable Compositions The components shown in Tables 2 and 3 were mixed together to prepare the photocurable compositions of Examples 1 to 16 and Comparative Example 1. The amount of each component in Tables 2 and 3 is in parts by mass, and blank spaces indicate that the corresponding component was not contained.

[0194] <Viscosity of Photocurable Composition> The viscosity of each photocurable composition prepared above was measured using an E-type viscometer (HAAKE MARS40 rheometer, manufactured by Thermo Fisher Scientific) at 25°C and 50 rpm. As a result, the viscosities of the photocurable compositions of Examples 1 to 16 and Comparative Example 1 were all within the range of 10 mPa·s to 15,000 mPa·s.

[0195] <Preparation of Various Test Pieces as Stereolithographic Objects> Using the photocurable composition described above, various test pieces (specifically, bending test pieces and toughness test pieces) were prepared as stereolithographic objects. Details are given below.

[0196] (Preparation of bending test specimens) Using a 3D printer (Cara Print 4.0 pro, manufactured by Kulzer), the photocurable composition was irradiated with light having a wavelength of 385 nm at an irradiation dose of 15 mJ / cm. ２ The photoresist was irradiated with 100 μm of UV light to form a cured layer with a thickness of 100 μm. This cured layer was then laminated in the thickness direction to obtain a 64 mm long, 10 mm wide, and 3.3 mm thick object. The resulting object was immersed in isopropyl alcohol (IPA) and cleaned for 5 minutes using an ultrasonic cleaner. The cleaned object was then dried with an air blower, and then placed in a post-curing device (Cara Print LEDcure, manufactured by Kulzer) and irradiated with visible light at 80°C for 20 minutes to obtain a rectangular plate-shaped bending test piece with a length of 64 mm, a width of 10 mm, and a thickness of 3.3 mm.

[0197] (Preparation of Toughness Test Piece) A rectangular plate-shaped toughness test piece having a length of 39 mm, a width of 8 mm and a thickness of 4 mm was obtained as a stereolithography object in the same manner as in the preparation of the bending test piece, except for the size of the test piece.

[0198] <Evaluation of Stereolithography> The following evaluations of the stereolithography were carried out using the bending test pieces and toughness test pieces. The results are shown in Tables 2 and 3.

[0199] (Flexural Modulus) The flexural modulus of the above-mentioned flexural test piece was measured in accordance with ISO 20795-1:2013. This measurement was performed using a tensile tester (manufactured by Intesco Corporation). Based on the obtained flexural modulus (MPa), the flexural modulus was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most excellent flexural modulus is ranked A.

[0200] - Evaluation criteria for flexural modulus - A: The flexural modulus was 1800 MPa or more. B: The flexural modulus was 1500 MPa or more and less than 1800 MPa. C: The flexural modulus was less than 1500 MPa.

[0201] (Toughness) The above toughness test specimen was subjected to a fracture toughness test by bending test in accordance with ISO 20795-1:2013, and the total work of fracture (J / m ２ The total work of fracture (J / m) was measured. This measurement was also carried out using a tensile tester (manufactured by Intesco Co., Ltd.). ２ ) and the toughness was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most excellent toughness is ranked A.

[0202] - Toughness evaluation criteria - A: Total fracture work is 500 J / m ２ B: Total work of destruction was 200 J / m or more. ２ More than 500J / m ２ C: Total work of fracture was less than 200 J / m ２ It was less than.

[0203]

[0204]

[0205] As shown in Tables 2 and 3, Examples 1 to 16, which used the urethane (meth)acrylate compound represented by formula (1), had superior toughness of the stereolithography objects compared to Comparative Example 1, which used the conventionally used UDMA. Furthermore, Examples 1 to 16 maintained the same level of flexural modulus of elasticity of the stereolithography objects compared to Comparative Example 1.

[0206] Next, an example of the second aspect will be described.

[0207] The abbreviations for the compounds used in the production of the urethane (meth)acrylate compound represented by formula (1) (monomer A described below) have the same meanings as those in the examples of the first aspect.

[0208] <Production of Monomer A as Urethane (Meth)acrylate Compound Represented by Formula (1)> The following Monomer A was produced as a specific example of the urethane (meth)acrylate compound represented by Formula (1). Monomer A in this Example of the Second Aspect corresponds to Monomer 2 in the Example of the First Aspect.

[0209]

[0210] The details of the production method for Monomer A are described below. Newpol BP-3P (100 g) and XDI (83.28 g, 0.44 mol) were placed in a 0.5-liter four-neck flask (hereinafter also referred to as the "reactor") equipped with a thoroughly dried stirring blade and thermometer, and the temperature was raised to 50°C and stirring was continued. Subsequently, DBTDL (0.18 g, 0.29 mmol) was added as a polymerization catalyst. After the addition of DBTDL, the mixture was cooled so that the reaction temperature was 50 to 80°C, and then heated to 90°C. After the reaction was carried out for 3 hours, BHT (0.48 g, 2.18 mmol) was added as a polymerization inhibitor and stirred until the mixture became homogeneous. Then, HEMA (52.44 g, 0.40 mol) was added dropwise over 30 minutes, and the reaction was carried out at 90°C for 4 hours. During this time, the progress of the reaction was monitored by liquid chromatography-mass spectrometry (LC-MS), and the end point of the reaction was confirmed. Specifically, LC-MS confirmed a decrease in the peak of Niupol BP-3P and an increase in the new peak of the above-mentioned Monomer A. In particular, LC-MS confirmed that the peak of Monomer A was detected between retention times of 14.0 and 24.0 minutes, (Monomer A peak area / HEMA peak area) was 26.8, and the mass of Monomer A was detected from 981 to 2751 as [M+H], and it was confirmed that x+y was 2 to 5 and n was 1 to 4. By discharging the product from the reactor, 235 g of Monomer A was obtained.

[0211] (Liquid Chromatography Mass Spectrometry (LC-MS) Conditions) In the production of Monomer A, LC-MS was performed using the following equipment and analysis conditions. LC-MS: ACQUITY UPLC H CLASS (manufactured by Waters Corporation) Column: ACQUITY UPLC BEH C18 1.7 μm 2.1×100 mm (manufactured by Waters Corporation) Flow rate: 0.5 ml / min Detection wavelength: 210 nm Mass spectrometry: electrospray spectrometry (ESI) Mobile phase: the following mobile phase

[0212] -Mobile phase- A mobile phase with a volume ratio of [acetonitrile containing 0.1% by mass of formic acid / water containing 0.1% by mass of formic acid] = 10 / 90 (0 min) → 100 / 0 (up to 20.0 min) → 10 / 90 (up to 25.0 min) → 10 / 90 (up to 35.0 min).

[0213] <Preparation of Monomer B, a Urethane Acrylate Compound> The following Monomer B, a urethane acrylate compound, was prepared.

[0214]

[0215] HEA (390 g, 3.36 mol), DBTDL (0.74 g (0.1% by mass relative to the total weight of HEA and NBDI)), and BHT (0.37 g (0.05% by mass relative to the total mass of HEA and NBDI)) were added to a 1-liter four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and after stirring until homogeneous, the mixture was heated to 60°C. Subsequently, NBDI (346 g, 1.68 mol) was added dropwise to the flask over 1 hour. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled so that the temperature remained below 80°C. After the entire amount of NBDI was added dropwise, the reaction temperature was maintained at 80°C and the reaction was carried out for 10 hours. The product was discharged from the reactor, yielding 700 g of Monomer B.

[0216] The abbreviations of the compounds used in producing Monomer B are as follows: HEA: 2-hydroxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd. DBTDL: dibutyltin dilaurate, manufactured by Tokyo Chemical Industry Co., Ltd. NBDI: norbornane diisocyanate, manufactured by Mitsui Chemicals, Inc. BHT: 2,6-di-tert-butyl-p-cresol, manufactured by Tokyo Chemical Industry Co., Ltd.

[0217] Examples 101 to 107, Comparative Example 101 Preparation of Photocurable Compositions The components were mixed in the amounts shown in Tables 4 to 6 to prepare the photocurable compositions of Examples 101 to 107 and Comparative Example 101. The amount of each component in Tables 4 to 6 is in parts by mass, and blank spaces indicate that the corresponding component was not contained.

[0218] The abbreviations of the compounds used in preparing the photocurable composition are listed below. <Urethane (meth)acrylate compound> UDMA... 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate ("genomer 4297" manufactured by Rahn AG) <(meth)acrylate compound not containing a urethane bond> TEGDMA... triethylene glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. <Photopolymerization initiator> CQ... camphorquinone, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. DMAB... 2-butoxyethyl 4-(dimethylamino)benzoate, manufactured by Tokyo Chemical Industry Co., Ltd. <Filler> Silica Filler A... silica glass (UltraFine G018-053 (manufactured by SCHOTT))

[0219] <Preparation of Bending Test Pieces as Cured Products of Photocurable Compositions> The photocurable compositions of each Example and Comparative Example were placed in a 2 mm x 2 mm x 25 mm silicone mold and irradiated with light for 3 minutes on each side (i.e., 6 minutes in total) using a visible light irradiation device (Solidilite V, manufactured by Shofu Co., Ltd.) to obtain cured products of the photocurable compositions. The obtained cured products were then heat-treated in an oven at 110°C for 15 minutes. After the heat treatment, the cured products were removed from the oven and cooled to room temperature. The cooled cured products were immersed in distilled water in a sealable sample container and kept at 37°C for 24 hours. The cured products after this 24-hour holding period were used as bending test pieces.

[0220] <Bending Test (Evaluation of Bending Strength)> Using the above bending test piece and a testing machine (manufactured by INTESCO), a three-point bending test was performed under conditions of a support distance of 20 mm and a crosshead speed of 1 mm / min. Based on each bending strength (MPa) obtained from the three-point bending test, the bending strength of the bending test piece, which was a cured product of the photocurable composition, was evaluated according to the following evaluation criteria. The results are shown in Tables 4 to 6. In the following evaluation criteria, the most excellent bending strength is ranked "A." Furthermore, rankings of "A" and "B" indicate superior bending strength compared to the comparative example.

[0221] -Evaluation criteria- A: The bending strength of the Example was +25 MPa or more relative to the bending strength of the comparative example for that Example. B: The bending strength of the Example was more than 0 MPa but less than +25 MPa relative to the bending strength of the comparative example for that Example. C: The bending strength of the Example was equal to or less than the bending strength of the comparative example for that Example.

[0222] Here, the comparative example for each example is, in principle, a comparative example in which all of the urethane (meth)acrylate compounds in that example are replaced with UDMA. However, for example 107, the comparative example in which all of the urethane (meth)acrylate compounds in example 107 are replaced with UDMA was difficult to prepare and could not be evaluated, so the comparative example for example 107 was comparative example 103, which had the highest bending strength among the comparative examples.

[0223] <Viscosity of Photocurable Composition> The viscosity of the photocurable composition of each Example and Comparative Example was measured using an E-type viscometer (HAAKE MARS40 rheometer, manufactured by Thermo Fisher Scientific) at 50 rpm and 80° C. The results are shown in Tables 4 to 6.

[0224]

[0225]

[0226]

[0227] As shown in Tables 4 to 6, the cured products of the photocurable compositions in each Example were superior in bending strength to the cured products of the photocurable compositions in the comparative examples.

[0228] The disclosures of Japanese Patent Application No. 2024-019017, filed on February 9, 2024, and Japanese Patent Application No. 2024-169433, filed on September 27, 2024, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A urethane (meth)acrylate compound represented by the following formula (1): [In formula (1), two R １ are each independently a divalent organic group, n Xs are each independently a divalent group represented by formula (X1), (n+1) Ys are each independently a divalent group represented by formula (Y1) or formula (Y2), and two R ２ are each independently a hydrogen atom or a methyl group, and n is an integer of 1 to 10. In formula (X1), R ＸＡ is a divalent hydrocarbon group containing a cyclic structure, and (m+k) R ＸＢ are each independently a divalent hydrocarbon group, m and k are each independently an integer of 1 to 5, and two *'s each indicate a bonding position. Ｙ１Ａ are each independently a linear alkylene group having 1 to 5 carbon atoms or a methylmethylene group, and R Ｙ１Ｂ is a divalent cyclic hydrocarbon group having 5 to 12 carbon atoms, and two *s each indicate a bonding position. Ｙ２Ａ is a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, and two * symbols each indicate a bonding position.

2. The urethane (meth)acrylate compound according to claim 1, wherein the divalent group represented by formula (Y1) is a divalent group represented by any one of the following formulae (Y1-1) to (Y1-7): [In each of formulas (Y1-1) to (Y1-7), two * indicate the bonding position.] 3. The urethane (meth)acrylate compound according to claim 1, having a molecular weight of 12,000 or less.

4. A monomer composition comprising the urethane (meth)acrylate compound according to any one of claims 1 to 3.

5. The monomer composition according to claim 4, which is a monomer composition for use as a material for an appliance to be worn in the oral cavity, a monomer composition for use as a material for a medical device component, a monomer composition for use as a material for a denture base, or a monomer composition for use as a material for a surgical component.

6. A photocurable composition comprising the urethane (meth)acrylate compound according to any one of claims 1 to 3 and a polymerization initiator.

7. The photocurable composition according to claim 6, which is used for producing a three-dimensional object by photolithography.

8. The photocurable composition according to claim 6, which is used to produce an instrument to be worn in the oral cavity, a medical device component, a denture base, or a surgical component.

9. A three-dimensional object made from the photocurable composition according to claim 6.

10. An appliance for use in the oral cavity, comprising the three-dimensional object according to claim 9.

11. A medical device member comprising the three-dimensional object according to claim 9.

12. A denture base comprising the three-dimensional object according to claim 9.

13. A surgical instrument comprising the three-dimensional object according to claim 9.

14. The photocurable composition according to claim 6, further comprising a filler.

15. The photocurable composition according to claim 14, wherein the content of the filler is 40% by mass to 90% by mass based on the total amount of the photocurable composition.

16. The photocurable composition according to claim 6, which has a viscosity of 10 mPa·s to 50,000 mPa·s as measured at 50 rpm and 80°C using an E-type viscometer.

17. The photocurable composition according to claim 6, which is a photocurable composition for dental materials.

18. A cured product of the photocurable composition according to claim 6.

19. A dental material comprising the photocurable composition according to claim 6 or a cured product thereof.

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