Monomer composition for stereolithography, photocurable composition for stereolithography, dental product, and method for producing stereolithographic object

Abstract

To provide a thio-urethane (meth)acrylate compound that enables imparting flexural strength to a cured product.SOLUTION: A thio-urethane (meth)acrylate compound comprising two linkages represented by formula (X), two urethane linkages, and two (meth)acryloyl groups, wherein in formula (X), the two * each indicate a bonding site.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a monomer composition for stereolithography, a photocurable composition for stereolithography, a dental product, and a method for producing a stereolithography object. [Background technology]

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

[0003] [Patent Document 1] Patent No. 4160311 Summary of the Invention [Problem to be solved by the invention]

[0004] In some cases, objects created using a 3D printer were not strong enough.

[0005] The problem to be solved by one aspect of the present disclosure is to provide a monomer composition for stereolithography and a photocurable composition for stereolithography that can impart excellent toughness to stereolithography objects, a dental product with excellent toughness, and a method for manufacturing a stereolithography object using the monomer composition for stereolithography. [Means for solving the problem]

[0006] Specific means for solving the above problems are as follows. <1> A monomer composition for stereolithography, comprising a (meth)acrylate compound (A) which is a reaction product of a thiol compound (B) containing two or more mercapto groups, a (meth)acrylate compound (C) containing one or more hydroxy groups and one or more (meth)acryloyloxy groups, and an isocyanate compound (D) containing two or more isocyanate groups. <2> The (meth)acrylate compound (A) contains a bond represented by the following formula (X), a urethane bond, and a (meth)acryloyloxy group: <1> The stereolithography monomer composition according to claim 1.

[0007] [ka]

[0008] In formula (X), the two *'s each represent a bonding position.

[0009] <3> the number of mercapto groups contained in the thiol compound (B) is 2 to 4, the number of isocyanate groups contained in the isocyanate compound (D) is two, The (meth)acrylate compound (A) contains a compound represented by the following formula (A1): <1> or <2> The stereolithography monomer composition according to claim 1.

[0010] [ka]

[0011] In formula (A1), R 1A is a residue obtained by removing all mercapto groups from the thiol compound (B), R 2A is a residue obtained by removing all isocyanate groups from the isocyanate compound (D), R 3A is a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from the (meth)acrylate compound (C), R 4Ais a hydrogen atom or a methyl group, n A is an integer between 2 and 4, n A R 2A may be the same or different, n A R 3A may be the same or different, n A R 4A may be the same or different.

[0012] <4> The isocyanate compound (D) includes a compound represented by any one of the following formulas (D1) to (D8): <1> ~ <3> 10. The stereolithography monomer composition according to claim 9, wherein the monomer composition is a mono- or di-fluoropolymer.

[0013] [ka]

[0014] <5> The thiol compound (B) includes a compound represented by any one of the following formulas (B1) to (B16): <1> ~ <4> 10. The stereolithography monomer composition according to claim 9, wherein the monomer composition is a mono- or di-fluoropolymer.

[0015] [ka]

[0016] In formula (B16), R B is a divalent organic group having 1 to 20 carbon atoms.

[0017] <6> The (meth)acrylate compound (C) contains a compound represented by the following formula (C1): <1> ~ <5> 10. The stereolithography monomer composition according to claim 9, wherein the monomer composition is a mono- or di-fluoropolymer.

[0018] [ka]

[0019] In formula (C1), R 1C is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R 2C is a hydrogen atom or a methyl group.

[0020] <7> <1> ~ <6> 1. A photocurable composition for stereolithography, comprising the monomer composition for stereolithography according to any one of 1 to 3 above and a photopolymerization initiator. <8> Further, the (meth)acrylate (E) is a (meth)acrylate other than the (meth)acrylate (A), <7> The photocurable composition for stereolithography according to claim 1. <9> The viscosity measured using an E-type viscometer at 25°C and 50 rpm is 5 mPa·s to 6000 mPa·s. <7> or <8> The photocurable composition for stereolithography according to claim 1. <10> Used as dental products, <7> ~ <9> 1. The photocurable composition for stereolithography according to claim 1 . <11> <7> ~ <10> A dental product comprising a stereolithographic object made from the photocurable composition for stereolithography described in any one of the above. <12> a step of obtaining a stereolithography monomer composition containing a (meth)acrylate compound (A) which is a reaction product of a thiol compound (B) containing two or more mercapto groups, a (meth)acrylate compound (C) containing one or more hydroxy groups and one or more (meth)acryloyloxy groups, and an isocyanate compound (D) containing two or more isocyanate groups; preparing a photocurable composition for stereolithography, the photocurable composition comprising the monomer composition for stereolithography and a photopolymerization initiator; obtaining a stereolithography product from the photocurable composition for stereolithography; A method for manufacturing a photo-fabricated object, comprising: [Effects of the Invention]

[0021] According to one aspect of the present disclosure, there are provided a monomer composition for stereolithography and a photocurable composition for stereolithography that can impart excellent toughness to a stereolithography object, a dental product with excellent toughness, and a method for manufacturing a stereolithography object using the monomer composition for stereolithography. DETAILED DESCRIPTION OF THE INVENTION

[0022] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. In the present disclosure, when there are multiple substances corresponding to each component, the amount of each component means the total amount of the multiple substances unless otherwise specified. In this disclosure, "(meth)acryloyl group" means acryloyl group and methacryloyl group, and "(meth)acrylate" means acrylate and methacrylate.

[0023] [Monomer composition for stereolithography] The monomer composition for stereolithography of the present disclosure contains a (meth)acrylate compound (A) that is a reaction product of a thiol compound (B) containing two or more mercapto groups, a (meth)acrylate compound (C) containing one or more hydroxy groups and one or more (meth)acryloyloxy groups, and an isocyanate compound (D) containing two or more isocyanate groups.

[0024] The stereolithography monomer composition of the present disclosure can impart excellent toughness to a stereolithography object produced using the composition. Here, the term "stereolithography object" refers to a stereolithography object formed by stereolithography using the disclosed monomer composition for stereolithography alone, or a photocurable composition for stereolithography containing the disclosed monomer composition for stereolithography and a photopolymerization initiator. That is, the stereolithographic object has excellent toughness. Stereolithography is preferably performed using a 3D printer.

[0025] According to the stereolithography monomer composition of the present disclosure, the viscosity of the stereolithography monomer composition alone, or of a photocurable composition for stereolithography containing the stereolithography monomer composition of the present disclosure and a photopolymerization initiator, can be maintained low enough to be suitable for use as a composition for 3D printers.

[0026] <(Meth)acrylate Compound (A)> The (meth)acrylate compound (A) contained in the stereolithography monomer composition of the present disclosure is a reaction product of a thiol compound (B) containing two or more mercapto groups, a (meth)acrylate compound (C) containing one or more hydroxy groups and one or more (meth)acryloyloxy groups, and an isocyanate compound (D) containing two or more isocyanate groups.

[0027] In order to further reduce the above-mentioned viscosity (i.e., the viscosity of the monomer composition for stereolithography of the present disclosure alone, or the viscosity of the photocurable composition for stereolithography containing the monomer composition for stereolithography of the present disclosure and a photopolymerization initiator), the upper limit of the molecular weight of the (meth)acrylate compound (A) is preferably 10,000 or less, more preferably 5,000 or less, even more preferably 3,000 or less, and even more preferably 2,000 or less. The lower limit of the molecular weight of the (meth)acrylate compound (A) is not particularly limited as long as it contains a (meth)acryloyloxy group.

[0028] The (meth)acrylate compound (A) preferably contains a bond represented by the following formula (X) (that is, a thiourethane bond), a urethane bond, and a (meth)acryloyloxy group. This allows the toughness of the resulting stereolithographic object to be further improved compared to when a (meth)acrylate compound containing a urethane bond and a (meth)acryloyloxy group but not a bond represented by formula (X) is used.

[0029] [ka]

[0030] In formula (X), the two *'s each represent a bonding position.

[0031] The thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D), which are raw materials for producing the (meth)acrylate compound (A), may each be used alone or in combination of two or more.

[0032] In Tables 1 to 10 in the Examples section described later, the thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D) are referred to as thiol (B), (meth)acrylate (C), and isocyanate (D), respectively.

[0033] Preferred embodiments of the thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D) are shown below.

[0034] <Thiol Compound (B)> The thiol compound (B) is a compound containing two or more mercapto groups. The number of mercapto groups contained in the thiol compound (B) is preferably two to four. When the number of mercapto groups contained in the thiol compound (B) is four or less, the viscosity described above (i.e., the viscosity of the stereolithography monomer composition of the present disclosure alone, or the viscosity of the stereolithography photocurable composition containing the stereolithography monomer composition of the present disclosure and a photopolymerization initiator) can be further reduced.

[0035] The molecular weight of the thiol compound (B) is preferably 1,000 or less, more preferably 600 or less.

[0036] The thiol compound (B) preferably includes a compound represented by any one of the following formulas (B1) to (B16).

[0037] [ka]

[0038] In formula (B16), R B is a divalent organic group having 1 to 20 carbon atoms.

[0039] The compound represented by formula (B16) preferably includes a thiol compound represented by any one of the following formulae (B16-1) to (B16-5).

[0040] [ka]

[0041] In formula (B16-1), R is a divalent hydrocarbon group having 1 to 20 carbon atoms. The divalent hydrocarbon group represented by R is preferably an alkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), an arylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (e.g., a phenylene group), an alkylenearylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (e.g., a methylenephenylene group), or an alkylenearylenealkylene group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (e.g., a methylenephenylenemethylene group). In formula (B16-4), n is an integer of 1 to 10.

[0042] The total proportion of the thiol compounds represented by any one of Formulas (B1) to (B16) in the thiol compound (B) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.

[0043] <(Meth)acrylate compound (C)> The (meth)acrylate compound (C) is a compound containing one or more hydroxy groups and one or more (meth)acryloyloxy groups.

[0044] The molecular weight of the (meth)acrylate compound (C) is preferably 1,000 or less, more preferably 500 or less, and even more preferably 400 or less.

[0045] The (meth)acrylate compound (C) is Preferably, the compound contains one hydroxy group and one (meth)acryloyloxy group, More preferably, it contains a compound represented by the following formula (C1).

[0046] [ka]

[0047] In formula (C1), R 1C is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R 2C is a hydrogen atom or a methyl group.

[0048] R 1C The divalent organic group represented by the formula (I) may contain a hydroxy group and a hydrocarbon group. R B The divalent organic group represented by the formula (I) may further contain an ester bond, an ether bond, a sulfide bond, or the like.

[0049] The proportion of the compound represented by formula (C1) in the (meth)acrylate compound (C) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.

[0050] Examples of the (meth)acrylate compound (C) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate.

[0051] The (meth)acrylate compound (C) preferably includes at least one selected from the group consisting of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxybutyl acrylate (2HBA), 2-hydroxybutyl methacrylate (2HBMA), 4-hydroxybutyl acrylate (4HBA), 4-hydroxybutyl methacrylate (4HBMA), 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, and 1,4-cyclohexanedimethanol monomethacrylate. The proportion of these compounds in the (meth)acrylate compound (C) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.

[0052] <Isocyanate compound (D)> The isocyanate compound (D) is a compound containing two or more isocyanate groups. The isocyanate compound (D) preferably includes a compound containing two isocyanate groups.

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

[0054] The isocyanate compound (D) preferably includes a compound containing two isocyanate groups, and more preferably includes a compound represented by any one of the following formulas (D1) to (D8).

[0055] [ka]

[0056] The total proportion of the compounds represented by any one of Formulas (D1) to (D8) in the isocyanate compound (D) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.

[0057] <Compound represented by formula (A1)> In the stereolithography monomer composition of the present disclosure, the number of mercapto groups contained in the thiol compound (B) is 2 to 4, The number of isocyanate groups contained in the isocyanate compound (D) is two, The (meth)acrylate compound (A) is preferably a compound represented by the following formula (A1).

[0058] [ka]

[0059] In formula (A1), R 1A is a residue obtained by removing all mercapto groups from a thiol compound (B) having 2 to 4 mercapto groups, R 2A is a residue obtained by removing all isocyanate groups from the isocyanate compound (D) when the number of isocyanate groups is two, R 3A represents a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from a (meth)acrylate compound (C) having one hydroxy group and one (meth)acryloyloxy group, R 4A is a hydrogen atom or a methyl group, n A is an integer between 2 and 4, n A R 2A may be the same or different, n A R 3Amay be the same or different, n A R 4A may be the same or different.

[0060] <Content of (meth)acrylate compound (A)> The content of the (meth)acrylate compound (A) relative to the total amount of the monomer composition for stereolithography of the present disclosure may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, 80% by mass or more, or 90% by mass or more. The upper limit of the content of the (meth)acrylate compound (A) relative to the total amount of the stereolithography monomer composition of the present disclosure may be, for example, 99 mass %, 95 mass %, or 90 mass %. For example, the stereolithography monomer composition of the present disclosure may be a composition containing 90% by mass or more of the (meth)acrylate compound (A) and impurities.

[0061] There are no particular limitations on the applications of the stereolithography monomer composition of the present disclosure. The stereolithography monomer composition of the present disclosure is preferably a monomer composition for dental materials. Specific examples of dental materials will be described later.

[0062] <Example of a method for producing a monomer composition for stereolithography (Production Method X)> An example of a manufacturing method for producing the stereolithography monomer composition of the present disclosure (hereinafter also referred to as "manufacturing method X") will be described below.

[0063] The production method X includes a step of reacting the above-mentioned thiol compound (B), the above-mentioned (meth)acrylate compound (C), and the above-mentioned isocyanate compound (D) to produce a (meth)acrylate compound (A) which is a reaction product of the above-mentioned thiol compound (B), the above-mentioned (meth)acrylate compound (C), and the above-mentioned isocyanate compound (D). The production method X may include other steps as necessary.

[0064] The above reaction in Production Method X may be carried out in the absence of a solvent or in a solvent. As the 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 of two or more.

[0065] (catalyst) In the above reaction in Production Method X, a catalyst may be used. Examples of catalysts include: Organotin compounds such as dibutyltin dilaurate, dibutyltin dioctate, and tin octoate; Other organometallic compounds other than tin, such as copper naphthenate, cobalt naphthenate, zinc naphthenate, zirconium acetylacetonate, iron acetylacetonate, and germanium acetylacetonate; amine compounds and salts thereof, 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; trialkylphosphine compounds, such as tri-n-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine, and tri-n-octylphosphine; Examples include: Of these, dibutyltin dilaurate and tin octoate are preferred.

[0066] The amount of the catalyst used may be 0.001% by mass to 1.0% by mass, or 0.01% by mass to 0.5% by mass, based on the total amount of the thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D).

[0067] The reaction temperature is not particularly limited and is, for example, 20°C to 120°C, preferably 30°C to 100°C, and more preferably 50°C to 100°C.

[0068] 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).

[0069] During the above reaction in Production Method X, a polymerization inhibitor may be used. Examples of the polymerization inhibitor include dibutylhydroxytoluene (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), and phenothiazine (PTZ).

[0070] 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 amount of the thiol compound (B), the (meth)acrylate compound (C), and the isocyanate compound (D).

[0071] [Photocurable composition for stereolithography] The curable composition for stereolithography according to the present disclosure contains the monomer composition for stereolithography according to the present disclosure and a polymerization initiator. The curable composition for stereolithography according to the present disclosure may contain other components.

[0072] The curable composition for stereolithography of the present disclosure contains the monomer composition for stereolithography of the present disclosure, and therefore exhibits the same effect as that of the monomer composition for stereolithography of the present disclosure (i.e., the effect of imparting excellent toughness to a stereolithography object).

[0073] The proportion of the monomer composition for stereolithography of the present disclosure in the curable composition for stereolithography of the present disclosure may be 10% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, 80% by mass or more, or 90% by mass or more.

[0074] <Photopolymerization initiator> The curable composition for stereolithography according to the present disclosure contains at least one photopolymerization initiator. As the photopolymerization initiator, for example, a general photopolymerization initiator used in the field of stereolithography can be used. 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, phenyl glyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, iron phthalocyanine compounds, benzoin ether compounds, and anthraquinone compounds.

[0075] The photopolymerization initiator preferably contains at least one selected from the group consisting of alkylphenone compounds and acylphosphine oxide compounds. In order to further improve the modeling accuracy of the stereolithography object, the photopolymerization initiator is More preferably, the compound 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)}.

[0076] The amount of photopolymerization initiator contained in the photocurable composition for stereolithography is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the monomer composition for stereolithography.

[0077] <(Meth)acrylate compound (E)> The photocurable composition for stereolithography according to the present disclosure may contain a (meth)acrylate compound (E) that is a (meth)acrylate compound other than the (meth)acrylate compound (A).

[0078] Examples of the (meth)acrylate compound (E) include neopentyl di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol Examples include chol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (note: a compound known as "urethane dimethacrylate (UDMA)"). The (meth)acrylate compounds (E) may be used alone or in combination of two or more.

[0079] For example, in order to adjust the viscosity of the photocurable composition for stereolithography to a low level, a viscosity adjusting monomer such as triethylene glycol dimethacrylate may be used. In this case, the viscosity-adjusting monomer and the (meth)acrylate compound (A) may be used in a mass ratio of 1:0.8 to 1.2.

[0080] When the photocurable composition for stereolithography according to the present disclosure contains a (meth)acrylate compound (E), the proportion of the (meth)acrylate compound (E) in the photocurable composition for stereolithography is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and even more preferably 20% by mass to 60% by mass. When the photocurable composition for stereolithography of the present disclosure contains a (meth)acrylate compound (E), the proportion of the (meth)acrylate compound (A) in the photocurable composition for stereolithography is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and even more preferably 40% by mass to 80% by mass.

[0081] <Other ingredients> The curable composition for stereolithography according to the present disclosure may contain components other than the above-mentioned components, as needed. Other components include colorants, inorganic fillers, modifiers, stabilizers, antioxidants, solvents, and the like.

[0082] From the viewpoint of further improving the modeling accuracy of stereolithography objects, the curable composition for stereolithography according to the present disclosure does not contain an inorganic filler (e.g., silica, barium borosilicate glass, etc.; the same applies below), or if it contains an inorganic filler, the content of the inorganic filler relative to the total amount of the curable composition for stereolithography is preferably 10% by mass or less (more preferably 5% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less).

[0083] <Preferable viscosity of the curable composition for stereolithography> The curable composition for stereolithography according to the present disclosure preferably has a viscosity (hereinafter simply referred to as "viscosity") of 5 mPa·s to 6000 mPa·s, as measured using an E-type viscometer at 25°C and 50 rpm. Here, rpm means revolutions per minute. When the viscosity is 5 mPa·s to 6000 mPa·s, the photocurable composition has excellent handleability when a three-dimensional object is produced by stereolithography. The viscosity is more preferably 5000 mPa·s or less, even more preferably 4000 mPa·s or less, even more preferably 3000 mPa·s or less, even more preferably 2000 mPa·s or less, and even more preferably 1500 mPa·s or less.

[0084] <Example of photolithography> The photocurable composition for stereolithography of the present disclosure can be used, for example, in liquid tank type (for example, DLP type or SLA type, preferably DLP type) stereolithography, inkjet type stereolithography, and the like.

[0085] In liquid tank type stereolithography, a portion of the photocurable composition for stereolithography (i.e., an uncured photocurable composition in a liquid state; the same applies below) contained in a liquid tank is cured by irradiating it with light to form a cured layer, and this operation is repeated to stack the cured layers, thereby obtaining a stereolithography object. Liquid tank type stereolithography differs from inkjet type stereolithography, which uses inkjet nozzles, in that it uses a liquid tank. Liquid vat-type stereolithography can be broadly divided into DLP (Digital Light Processing) and SLA (Stereolithography) methods. In the DLP method, a surface of light is irradiated onto a photocurable composition in a liquid vat. In the SLA method, a laser beam is scanned onto a photocurable composition in a liquid vat.

[0086] In an example of DLP type stereolithography, for example, a build table that is movable in the vertical direction; a tray (i.e., a liquid tank) disposed below the build table (on the gravity direction side; the same applies below), including a light-transmitting portion, and containing a photocurable composition; 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 light-transmitting portion of the tray; A 3D printer equipped with this (for example, "Cara Print4.0" manufactured by Kulzer, "Max UV" manufactured by Asiga, etc.) is used. In this example, first, a gap of one layer is provided between the build table and the tray, and this gap is filled with a photocurable composition. Next, the photocurable composition filled in the gap is irradiated with planar light from below through the light-transmitting portion of the tray, and the irradiated area is cured 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 the photocurable composition. Next, the photocurable composition filled in 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 operations, cured layers are stacked to produce a three-dimensional object. In this example, the produced three-dimensional object may be further cured by irradiating it with light.

[0087] <Applications of photocurable composition for stereolithography> There are no particular limitations on the applications of the photocurable composition for stereolithography of the present disclosure. The photocurable composition for stereolithography according to the present disclosure is preferably a photocurable composition for stereolithography used in the production of dental products, from the viewpoint of more effectively improving the toughness of stereolithography objects. Dental products include dentures (i.e., artificial teeth), denture bases, dental prostheses, medical instruments used in the oral cavity, dental models, models for lost-lose casting, and the like. Dental prostheses include inlays, crowns, bridges, temporary crowns, temporary bridges, and the like. Medical devices used in the oral cavity include mouthpieces, mouthguards, orthodontic appliances, occlusal splints, impression trays, surgical guides, and the like. Examples of dental models include tooth and jaw models.

[0088] [Dental products] The dental product of the present disclosure includes a stereolithographic object made from the photocurable composition for stereolithography of the present disclosure. Therefore, the dental product of the present disclosure has excellent toughness. Specific examples of dental products are described above.

[0089] [Method for manufacturing a photo-fabricated object] The method for manufacturing a stereolithography object according to the present disclosure includes: a step of obtaining a stereolithography monomer composition containing a (meth)acrylate compound (A) which is a reaction product of a thiol compound (B) containing two or more mercapto groups, a (meth)acrylate compound (C) containing one or more hydroxy groups and one or more (meth)acryloyloxy groups, and an isocyanate compound (D) containing two or more isocyanate groups; A step of preparing a photocurable composition for stereolithography, the photocurable composition including a monomer composition for stereolithography and a photopolymerization initiator; obtaining a stereolithography product from the photocurable composition for stereolithography; Includes: The method for producing a stereolithographic object according to the present disclosure may include other steps as necessary.

[0090] According to the method for manufacturing a stereolithography object of the present disclosure, a stereolithography object with excellent toughness can be manufactured.

[0091] For the step of obtaining the stereolithography monomer composition, the above-mentioned Production Method X can be referred to. In the step of preparing the photocurable composition for stereolithography, a monomer composition for stereolithography and a photopolymerization initiator may be mixed by a known method. The above-mentioned known optical shaping techniques can be applied to the process of obtaining a stereolithographic object. [Example]

[0092] 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.

[0093] The abbreviations for the compounds used in the examples are shown below. <Thiol Compound (B)> T1: Pentaerythritol tetrakis(3-mercaptopropionate) (compound represented by the above formula (B2)) T2: A mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (a mixture of the compounds represented by the above formulae (B5) to (B7)) T3: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (the compound represented by the above formula (B10)) T4: 3,6-Dioxa-1,8-octanedithiol (a compound represented by the above formula (B16) (more specifically, formula (B16-2))) T5: 3,7-Dithia-1,9-nonanedithiol (a compound represented by the above formula (B16) (more specifically, formula (B16-3))) <(Meth)acrylate compound (C)> HEA: 2-hydroxyethyl acrylate HPA: 2-hydroxypropyl acrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate <Isocyanate compound (D)> XDI: m-Xylylene diisocyanate (compound represented by the above formula (D1)) TMXDI: 1,3-tetramethylxylylene diisocyanate (compound represented by the above formula (D3)) NBDI: A mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (the compound represented by the above formula (D2)) H6XDI: 1,3-bis(isocyanatomethyl)cyclohexane (compound represented by the above formula (D4)) <(Meth)acrylate compound (E)> TEGDMA: Triethylene glycol dimethacrylate <Photopolymerization initiator> Omnirad 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, manufactured by IGM RESINS BV <Reaction catalyst> DBTDL: Dibutyltin dilaurate <Polymerization inhibitor> BHT: Dibutylhydroxytoluene

[0094] <Method for Evaluating Viscosity of Photocurable Composition for Stereolithography> The viscosity of each of the photocurable compositions for stereolithography in the examples and comparative examples was measured using a rheometer (Thermo Fisher Scientific HAAKE MARS 40) and a parallel plate jig with a diameter of 25 mm at a measurement temperature of 25°C and a rotation speed of 50 rpm. Based on the obtained viscosity, the viscosity of each photocurable composition for stereolithography was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most desirable rank for the viscosity of the photocurable composition for stereolithography is "A," which is the lowest viscosity rank.

[0095] -Evaluation criteria for viscosity of stereolithography compositions- A: The viscosity of the photocurable composition for stereolithography is 5 mPa·s or more but less than 300 mPa·s B: The viscosity of the photocurable composition for stereolithography is 300 mPa·s or more and less than 2000 Pa·s C: The viscosity of the photocurable composition for stereolithography is 2000 mPa·s or more and 6000 Pa·s or less D: The viscosity of the photocurable composition for stereolithography exceeds 6000 mPa·s

[0096] <Evaluation of toughness of stereolithography objects (fracture toughness test)> A stereolithography object was fabricated using each of the photocurable compositions for stereolithography in the Examples and Comparative Examples, and the resulting stereolithography object was subjected to a fracture toughness test. Based on the results, the toughness was evaluated. Details are given below. The photocurable composition for stereolithography was applied to a 3D printer (Kulzer, Cara Print 4.0) using visible light at a wavelength of 405 nm and an illuminance of 14 mJ / cm. 2 The resulting object was irradiated with ultraviolet light of 365 nm wavelength at 10 J / cm. 2 The object was irradiated under the conditions of (a) to (c) and completely cured, thereby obtaining a photo-fabricated object. The resulting stereolithography product (hereinafter referred to as "test piece") was notched in accordance with ISO20795-1:2008, and then stored in a constant temperature water bath at 37±1°C for 7 days±2 hours. The test specimen was then removed from the constant temperature water bath and subjected to a fracture toughness test using a bending test in accordance with ISO20795-1:2008 to measure the total work of fracture (J / m 2 The fracture toughness test by bending test (i.e., measurement of total work of fracture) is a universal test. The test was carried out using a press (manufactured by Intesco Co., Ltd.) at a pressing speed of 1.0±0.2 mm / min. The obtained total fracture work value was evaluated according to the following evaluation criteria and used as an index of toughness. Based on the obtained total work of fracture, the toughness of the stereolithography object was evaluated according to the following evaluation criteria. In the following evaluation criteria, the rank of the stereolithography product with the best toughness is "AA." The ranks "AA," "A," "B," and "C" indicate superior toughness compared to the comparative example.

[0097] AA: The total work of destruction of the example is +20 J / m compared to the total work of destruction of the comparative example 2 That was all. A: The total work of destruction of the example is +10 J / m compared to the total work of destruction of the comparative example. 2 More than +20J / m 2 It was less than. B: The total work of fracture of the example is +5 J / m compared to the total work of fracture of the comparative example. 2 More than +10J / m2 It was less than. C: The total work of fracture of the example is 0 J / m compared to the total work of fracture of the comparative example. 2 Super +5J / m 2 It was less than. D: The total work of fracture of the example was equal to or less than the total work of fracture of the comparative example to which that example was compared.

[0098] Here, the comparative example for each example is, in principle, a comparative example in which the thiol (B) is omitted from the raw material of the (meth)acrylate (A) in the example. However, in Examples 601 to 604 and Example 801, when the thiol (B) was removed from the raw material of the (meth)acrylate (A), crystallization occurred and evaluation was impossible. Therefore, the comparative example for Examples 601 to 604 and Example 801 was Comparative Example 104, which had the highest total work of fracture among the comparative examples.

[0099] Example 1 DBTDL (0.1 parts by mass), BHT (0.05 parts by mass), XDI (21.06 parts by mass; approximately 0.112 moles) as the isocyanate compound (D), and T1 (2.73 parts by mass; approximately 0.0056 moles) as the thiol compound (B) were placed in a 100 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer and dissolved to form a homogeneous solution. The resulting homogeneous solution was reacted at 80°C for 4 hours to obtain a solution containing the intermediate. The resulting solution was heated to 90°C, and HPA (26.21 parts by mass; approximately 0.201 mol) as the (meth)acrylate compound (C) was added dropwise over 1 hour. Because the internal temperature rose due to the heat of reaction during the addition, the amount added was controlled to keep the temperature below 90°C. After the entire amount of HPA (26.21 parts by mass) was added dropwise, the reaction temperature was maintained at 90°C and the reaction was carried out for 10 hours. The progress of the reaction was monitored by HPLC analysis, and the end point of the reaction was confirmed. The product was discharged from the reactor to obtain a stereolithography monomer composition (50 g) containing a specific example of the (meth)acrylate compound (A) (in this Example 1, the reaction product of XDI, T1, and HPA). The obtained monomer composition for stereolithography (50 parts by mass), TEGDMA (50 parts by mass) as the (meth)acrylate compound (E), and Omnirad819 (2 parts by mass) as the photopolymerization initiator were mixed to obtain a photocurable composition for stereolithography. Using the obtained photocurable composition for stereolithography, the viscosity of the photocurable composition for stereolithography and the toughness of the stereolithography product were evaluated. The results are shown in Table 1.

[0100] [Examples 2 and 3, and Comparative Example 1 (Comparative Example)] The same procedure as in Example 1 was carried out, except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 1. The results are shown in Table 1.

[0101] [Examples 101 and 102, and Comparative Example 101 (Comparative Example)] The same procedure as in Example 1 was carried out, except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 2. The results are shown in Table 2.

[0102] [Examples 201 and 202, and Comparative Example 201 (Comparative Example)] The same procedure as in Example 1 was carried out except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 3. The results are shown in Table 3.

[0103] [Example 301 and Comparative Example 301 (Comparative Example)] The same procedure as in Example 1 was carried out, except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 4. The results are shown in Table 4.

[0104] [Examples 401 to 405 and Comparative Example 401 (Comparative Example)] The same procedure as in Example 1 was carried out, except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 5. The results are shown in Table 5.

[0105] [Examples 501 and 502, and Comparative Example 501 (Comparative Example)] The same procedure as in Example 1 was carried out except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 6. The results are shown in Table 6.

[0106] [Examples 601 to 604 and Comparative Example 401 (Comparative Example)] The same procedure as in Example 1 was carried out, except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 7. The results are shown in Table 7. - Regarding (※1) in Table 7 - As mentioned above, when the reaction was carried out by removing thiol (B) from the raw material of (meth)acrylate (A) in Examples 601 to 604, crystallization occurred and evaluation was impossible. Therefore, the comparative example for Examples 601 to 604 was Comparative Example 401, which had the highest total work of fracture among the comparative examples.

[0107] [Examples 701 and 702, and Comparative Example 701 (Comparative Example)] The same procedure as in Example 1 was carried out, except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 8. The results are shown in Table 8.

[0108] [Example 801 and Comparative Example 401 (Comparative Example)] The same procedure as in Example 1 was carried out, except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 9. The results are shown in Table 9. - Regarding (※1) in Table 9 - As mentioned above, when the reaction was carried out by removing thiol (B) from the raw material of (meth)acrylate (A) in Example 801, crystallization occurred and evaluation was impossible. Therefore, the comparative example for Example 801 was Comparative Example 401, which had the highest total work of fracture among the comparative examples.

[0109] [Examples 901 to 903 and Comparative Example 901 (Comparative Example)] The same procedure as in Example 1 was carried out, except that the raw materials for the (meth)acrylate compound (A) were changed as shown in Table 10. The results are shown in Table 10.

[0110] [Table 1]

[0111] [Table 2]

[0112] [Table 3]

[0113] [Table 4]

[0114] [Table 5]

[0115] [Table 6]

[0116] [Table 7]

[0117] [Table 8]

[0118] [Table 9]

[0119] [Table 10]

[0120] As shown in Tables 1 to 10, each example using a monomer composition for stereolithography containing a (meth)acrylate compound (A) which is a reaction product of a thiol compound (B) containing two or more mercapto groups, a (meth)acrylate compound (C) containing one or more hydroxyl groups and one or more (meth)acryloyloxy groups, and an isocyanate compound (D) containing two or more isocyanate groups, had superior toughness of the stereolithography object compared to the control comparative example in which the thiol compound (B) was omitted from the raw materials of the (meth)acrylate compound (A). Furthermore, the photocurable compositions for stereolithography in each of the Examples had low viscosities, similar to the photocurable compositions for stereolithography in the Comparative Examples.

Claims

1. A monomer composition for stereolithography, comprising a (meth)acrylate compound (A) which is a reaction product of a thiol compound (B) containing two or more mercapto groups, a (meth)acrylate compound (C) containing one or more hydroxy groups and one or more (meth)acryloyloxy groups, and an isocyanate compound (D) containing two or more isocyanate groups.

2. The stereolithography monomer composition according to claim 1 , wherein the (meth)acrylate compound (A) contains a bond represented by the following formula (X), a urethane bond, and a (meth)acryloyloxy group: 【Chemical 1】 [In formula (X), each of the two * marks represents a bonding position.]

3. the number of mercapto groups contained in the thiol compound (B) is 2 to 4, the number of isocyanate groups contained in the isocyanate compound (D) is two, The stereolithography monomer composition according to claim 1 , wherein the (meth)acrylate compound (A) includes a compound represented by the following formula (A1): 【Chemistry 2】 [In formula (A1), R １Ａ is a residue obtained by removing all mercapto groups from the thiol compound (B), R ２Ａ is a residue obtained by removing all isocyanate groups from the isocyanate compound (D), R ３Ａ represents a residue obtained by removing one hydroxy group and one (meth)acryloyloxy group from the (meth)acrylate compound (C), R ４Ａ is a hydrogen atom or a methyl group, n Ａ is an integer from 2 to 4, n Ａ R ２Ａ may be the same or different, n Ａ R ３Ａ may be the same or different, n Ａ R ４Ａ may be the same or different.

4. 2. The stereolithography monomer composition according to claim 1, wherein the isocyanate compound (D) includes a compound represented by any one of the following formulas (D1) to (D8): 【Chemistry 3】

5. 2. The stereolithography monomer composition according to claim 1, wherein the thiol compound (B) comprises a compound represented by any one of the following formulas (B1) to (B16): 【Chemistry 4】 [In formula (B16), R Ｂ is a divalent organic group having 1 to 20 carbon atoms.

6. The stereolithography monomer composition according to claim 1 , wherein the (meth)acrylate compound (C) includes a compound represented by the following formula (C1): 【Chemistry 5】 [In formula (C1), R １Ｃ is an organic group having 2 to 25 carbon atoms and containing one hydroxy group, R ２Ｃ is a hydrogen atom or a methyl group.

7. A photocurable composition for stereolithography, comprising the monomer composition for stereolithography according to any one of claims 1 to 6 and a photopolymerization initiator.

8. The photocurable composition for stereolithography according to claim 7 , further comprising a (meth)acrylate (E) other than the (meth)acrylate (A).

9. 8. The photocurable composition for stereolithography according to claim 7, wherein the viscosity measured at 25° C. and 50 rpm using an E-type viscometer is 5 mPa·s to 6000 mPa·s.

10. The photocurable composition for stereolithography according to claim 7, which is used as a dental product.

11. A dental product comprising a stereolithographic object made from the photocurable composition for stereolithography according to claim 7 .

12. a step of obtaining a stereolithography monomer composition containing a (meth)acrylate compound (A) which is a reaction product of a thiol compound (B) containing two or more mercapto groups, a (meth)acrylate compound (C) containing one or more hydroxy groups and one or more (meth)acryloyloxy groups, and an isocyanate compound (D) containing two or more isocyanate groups; preparing a photocurable composition for stereolithography, the photocurable composition comprising the monomer composition for stereolithography and a photopolymerization initiator; obtaining a stereolithography product from the photocurable composition for stereolithography; A method for manufacturing a photo-fabricated object, comprising:

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