Resin composition

Abstract

Provided is a resin composition containing a monofunctional oxetane compound (A), an aromatic bisoxetane compound (B), and a polycarbonate polyol (C). The polycarbonate polyol (C) content is 1-25 mass% relative to the total mass of the resin composition. The resin composition is used in 3D printer applications.

Description

resin composition

[0001] The present invention relates to a resin composition.

[0002] Epoxy-based photocurable resin compositions are known as one type of resin composition used in stereolithography 3D printers. Conventional epoxy-based photocurable resin compositions have the drawback of slow reaction rates and long modeling times due to their curing using cationic polymerization. However, photocurable resin compositions containing oxetane compounds have been disclosed as a method for producing shaped objects with high productivity by shortening the exposure time to active energy rays, due to their high curing sensitivity to active energy rays (see Patent Documents 1 and 2).

[0003] JP 2013-023574 A JP 2007-332294 A

[0004] However, the cured product of the resin composition has insufficient elongation, and therefore is brittle and easily breaks when used in a stereolithography 3D printer.Furthermore, the cured product tends to have a high yellow color, and when used in a stereolithography 3D printer, the appearance of the molded product is easily damaged.

[0005] An object of the present invention is to provide a resin composition that has high elongation and low yellowness after curing.

[0006] The present invention includes the following aspects: [Item 1] A resin composition comprising a monofunctional oxetane compound (A), an aromatic bisoxetane compound (B), and a polycarbonate polyol (C), wherein the content of the polycarbonate polyol (C) is 1 to 25 mass% relative to the total mass of the resin composition. [Item 2] The resin composition according to Item 1, which is for use in a 3D printer. [Item 3] The resin composition according to Item 1 or 2, wherein the aromatic bisoxetane compound (B) comprises 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl. [Item 4] The resin composition according to any one of Items 1 to 3, wherein the content of the aromatic bisoxetane compound (B) is 1 to 50 mass% relative to the total mass of the resin composition. [Item 5] The resin composition according to any one of Items 1 to 4, which comprises an acid generator. [Item 6] The polycarbonate polyol is a compound represented by the following formula: [In the formula, R Ｘ [Item 7] The resin composition according to any one of Items 1 to 5, wherein the compound has one or two or more repeating structural units represented by the formula (C1), and the total number of hydroxy groups at the molecular chain terminals is two or more. Ｘ and each occurrence is independently a linear divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms, a divalent branched aliphatic hydrocarbon group having 4 to 10 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group having 6 to 10 carbon atoms. [Item 8] The resin composition according to any one of Items 1 to 7, further comprising an epoxy group-containing compound (D). [Item 9] The resin composition according to Item 8, wherein the epoxy group-containing compound (D) has an alicyclic structure. [Item 10] The resin composition according to any one of Items 1 to 9, further comprising a (meth)acrylic acid ester (E). [Item 11] The resin composition according to any one of Items 1 to 10, having a viscosity of 50 to 1000 mPa s. [Item 12] A cured resin obtained by curing the resin composition according to any one of Items 1 to 11. [Item 13] The cured resin product according to Item 12, having a tensile elongation of 10% or more and a YI of 10 or less at a thickness of 1.0 mm, as measured according to JIS K7127. [Item 14] The cured resin product according to Item 13, having a haze of 10% or less at a thickness of 1.0 mm.

[0007] The present invention can provide a resin composition that has high elongation and low yellowness after curing.

[0008] <Definition of Terms> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. Furthermore, an "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0009] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C １－２０ Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents. The phrase "independently in each occurrence" means that, for each repeating structural unit, each group may be independently the same or different.

[0010] As used herein, the term "reactive group" refers to a functional group that is more reactive than an aliphatic saturated hydrocarbon group in various reactions such as nucleophilic attack, electrophilic attack, substitution reaction, elimination reaction, rearrangement reaction, radical reaction, etc. Examples of such functional groups include, but are not limited to, an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, an isocyanate group, a blocked isocyanate group, a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an alkali metal or alkaline earth metal base of a carboxylic acid, sulfonic acid, or phosphoric acid, an ammonium base with a counter anion of chlorine, bromine, or iodine ion, and other ionic groups.

[0011] It will be understood that the chemical structures described herein do not encompass chemical structures that would be recognized by those skilled in the art as being chemically impossible or extremely unstable.

[0012] <Resin Composition> The composition of the present invention will now be described.

[0013] The resin composition of the present invention comprises a monofunctional oxetane compound (A), an aromatic bisoxetane compound (B), and a polycarbonate polyol (C), and the content of the polycarbonate polyol (C) is 1 to 25 mass% based on the total mass of the resin composition.

[0014] The resin composition of the present invention can be used in a wide range of applications, but due to its properties, it is preferably used for 3D printer applications. Among 3D printers, it is more preferably used in stereolithography. Stereolithography methods include free-surface stereolithography (SLA) methods, regulated-surface stereolithography (SLA) methods, regulated-surface digital light processing (DLP) methods, regulated-surface liquid crystal (LCD) methods, and material jetting (MJ) methods. Among these, it is particularly preferably used in free-surface stereolithography (SLA) methods.

[0015] <Monofunctional oxetane compound (A)> In the present invention, the monofunctional oxetane compound (A) is a compound having one oxetane ring (oxetanyl group) in its molecular structure. In a preferred embodiment, the monofunctional oxetane compound (A) is a compound represented by the following formula: [In the formula, R ａ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ｂ is a monovalent organic group that does not have an oxetane ring.

[0016] R ａ is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0017] The hydrocarbon group is preferably an alkyl group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. In a particularly preferred embodiment, R ａ is an ethyl group.

[0018] R ｂ is a monovalent organic group that does not have an oxetane ring.

[0019] The monovalent organic group may be any monovalent organic group that does not have an oxetane ring, as long as the monofunctional oxetane compound (A) can exist stably. The monovalent organic group may be, for example, an alkyl group optionally interrupted by one or more oxygen atoms, preferably a C1-C6 alkyl or alkenyl group optionally interrupted by one or more oxygen atoms, more preferably a hydroxymethyl group, a 4-hydroxybutoxymethyl group, or a chloromethyl group, and even more preferably a hydroxymethyl group.

[0020] In one embodiment, R ｂ may have one or more of various functional groups and / or bonds. The types of such functional groups are not particularly limited, but examples include alkyl groups, cycloalkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, alkylene groups, hydroxy groups, alkoxy groups, aldehyde groups, carboxyl groups, carbonyl groups, nitro groups, amino groups, cyano groups, sulfo groups, aryl groups, and (meth)acrylic groups. The types of such bonds are not particularly limited, but examples include ether bonds, ester bonds, and amide bonds. In one embodiment, R ｂ has a hydroxy group.

[0021] In one embodiment, R ｂ is -CH ２ It's OH.

[0022] The content of the monofunctional oxetane compound (A) is not particularly limited, and may be, for example, 0.5% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, relative to the total mass of the resin composition of the present invention. Furthermore, the content may be, for example, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 25% by mass or less, relative to the total mass of the resin composition of the present invention. The content of the monofunctional oxetane compound (A) may be, for example, 0.5 to 50% by mass, preferably 1 to 40% by mass, and more preferably 1 to 30% by mass, relative to the total mass of the resin composition of the present invention. In one aspect, the content of the monofunctional oxetane compound (A) is 10 to 25% by mass, relative to the total mass of the resin composition of the present invention.

[0023] <Aromatic Bisoxetane Compound (B)>

[0024] In the present invention, the aromatic bisoxetane compound (B) is an aromatic compound having two oxetane rings. In a preferred embodiment, the aromatic bisoxetane compound (B) is represented by the following formula: [In the formula, R ｃ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ｄ is a divalent aromatic group.

[0025] R ｃ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0026] The hydrocarbon group is preferably an alkyl group. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. In a particularly preferred embodiment, R ｃ is an ethyl group.

[0027] R ｄ is a divalent aromatic group.

[0028] The divalent aromatic group can be any divalent organic group having one or more aromatic rings.

[0029] In a preferred embodiment, Rｄ has 1 to 6 aromatic rings. ｄ has 1 to 2, more preferably 2, aromatic rings.

[0030] The type of aromatic ring is not particularly limited, but examples thereof include aromatic rings having 6 to 20 carbon atoms. The aromatic ring may be a hydrocarbon ring or a ring containing a heteroatom within the ring. The aromatic ring may be monocyclic or polycyclic. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a furan ring, and a pyridine ring. In a preferred embodiment, the aromatic ring is a benzene ring. R ｄ When has two or more aromatic rings, the aromatic rings may be the same or different.

[0031] R ｄ may have one or more of various functional groups and / or bonds. The types of such functional groups are not particularly limited, but include, for example, alkyl groups, cycloalkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, alkylene groups, hydroxy groups, alkoxy groups, aldehyde groups, carboxyl groups, carbonyl groups, nitro groups, amino groups, cyano groups, sulfo groups, aryl groups, and oxo groups. The types of such bonds are also not particularly limited, but include, for example, ether bonds, ester bonds, and amide bonds. In one embodiment, R ｄ has a hydroxy group. ｄ has an oxo group. ｄ has an ether bond. ｄ When has two or more functional groups and / or bonds, the functional groups and / or bonds may be the same or different.

[0032] R ｄ As an example, preferably, the following formula: [In the formula, R １ are each independently an alkylene group having 1 to 6 carbon atoms; R ２ are each independently an alkylene group having 1 to 6 carbon atoms, -(R ３ O) ｎa divalent group represented by -, or -R ４ is a divalent group represented by C(=O)-, R ３ is independently in each occurrence an alkylene group having 2 to 5 carbon atoms; R ４ represents a single bond or an alkylene group having 1 to 6 carbon atoms, n represents an integer of 1 to 4, and in formula (B2), two R ２ may be bonded to any carbon atom on the benzene ring.

[0033] R １ are each independently an alkylene group having 1 to 6 carbon atoms.

[0034] R １ R may be linear or branched. １ R may be a substituted or unsubstituted alkylene group, but is preferably an unsubstituted alkylene group. １ Examples of R include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and a 1,2-dimethylethylene group. １ is preferably a methylene group.

[0035] R ２ are each independently an alkylene group having 1 to 6 carbon atoms, -(R ３ O) ｎ a divalent group represented by -, or -R ４ It is a divalent group represented by C(=O)-. ２ are preferably each independently an alkylene group having 1 to 6 carbon atoms.

[0036] R ２ The alkylene group having 1 to 6 carbon atoms in the formula (I) may be linear or branched, but is preferably linear. The alkylene group may be a substituted or unsubstituted alkylene group, but is preferably an unsubstituted alkylene group. Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and a 1,2-dimethylethylene group. The alkylene group is preferably a methylene group.

[0037] R ３ is independently in each occurrence an alkylene group of 2 to 5 carbon atoms.

[0038] R ３ The alkylene group having 2 to 5 carbon atoms in the formula (I) may be linear or branched. The alkylene group may be a substituted or unsubstituted alkylene group, but is preferably an unsubstituted alkylene group.

[0039] R ２ Ga-(R ３ O) ｎ When represented by -, the terminal oxygen atom of the repeating unit is directly bonded to any carbon atom of the benzene ring of formula (B2).

[0040] - (R ３ O) ｎ In the formula (I), n is an integer of 1 to 4, preferably an integer of 1 or 2.

[0041] R ２ - (R ３ O) ｎ Specific examples of the group represented by - include -CH ２ CH ２ O-, -CH ２ CH ２ CH ２ O-, -CH(CH ３ ) CH ２ O-, -CH ２ CH ２ OCH ２ CH ２ O-, etc.

[0042] R ４ is a single bond or an alkylene group having 1 to 6 carbon atoms.

[0043] R ４The alkylene group having 1 to 6 carbon atoms in the formula (I) may be linear or branched, but is preferably linear. The alkylene group may be a substituted or unsubstituted alkylene group, but is preferably an unsubstituted alkylene group. Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and a 1,2-dimethylethylene group. The alkylene group is preferably a methylene group.

[0044] R ２ Ga-R ４ Specific examples of C(=O)- include -C(=O)- and -CH ２ C(=O)-, -CH(CH ３ )C(=O)-,-CH ２ CH ２ C(=O)-, and the like.

[0045] In formula (B2), two R ２ may be bonded to any carbon atom on the benzene ring. ２ is preferably bonded at the para or meta position, and two R ２ is more preferably bonded at the meta position.

[0046] R other than the above ｄ More preferably, the compound is of the following formula: [In the formula, R ５ is independently in each occurrence an alkylene group having 1 to 6 carbon atoms, and m is an integer of 1 to 3.

[0047] R ５ is independently in each occurrence an alkylene group of 1 to 6 carbon atoms.

[0048] R ５ R may be linear or branched. ５ R may be a substituted or unsubstituted alkylene group, but is preferably an unsubstituted alkylene group. ５Examples of R include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and a 1,2-dimethylethylene group. ５ is preferably a methylene group.

[0049] In formula (B3), m is an integer of 1 to 3. In formula (B3), m is more preferably 1.

[0050] In a preferred embodiment, the aromatic bisoxetane compound (B) is 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl).

[0051] The content of the aromatic bisoxetane compound (B) is not particularly limited, and may be, for example, 0.5% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, relative to the total mass of the resin composition of the present invention. Furthermore, the content of the aromatic bisoxetane compound (B) may be, for example, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, relative to the total mass of the resin composition of the present invention. The content of the aromatic bisoxetane compound (B) may be, for example, 0.5 to 60% by mass, preferably 1 to 50% by mass, and more preferably 1 to 25% by mass, relative to the total mass of the resin composition of the present invention. In one aspect, the content of the aromatic bisoxetane compound (B) is 5 to 25% by mass, relative to the total mass of the resin composition of the present invention.

[0052] In the present invention, the monofunctional oxetane compound (A) and the aromatic bisoxetane compound (B) may each be used alone or in combination of two or more. For example, the resin composition of the present invention may contain one of the monofunctional oxetane compounds (A) and one of the aromatic bisoxetane compounds (B). Also, for example, the resin composition of the present invention may contain one of the monofunctional oxetane compounds (A) and two of the aromatic bisoxetane compounds (B).

[0053] <Polycarbonate polyol (C)> The polycarbonate polyol (C) can be synthesized by a known method, for example, by reacting one or more polyol monomers with a carbonate ester or phosgene. From the viewpoints of safety and handling of reagents, etc., polycarbonate polyols obtained by reacting one or more polyol monomers with a carbonate ester are preferred because they are easy to produce and do not produce terminal chlorinated products as by-products.

[0054] Known polyol monomers can be used as polyol monomers constituting the polycarbonate polyol. For example, aliphatic polyols such as linear aliphatic diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 1,9-nonanediol, and branched aliphatic diols such as 2-methyl-1,3-propanediol, 1,5-hexanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and neopentyl glycol; trifunctional or higher polyhydric alcohols such as trimethylolpropane and pentaerythritol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, and 2,5-bis(hydroxymethyl)methyl Examples of suitable polyols include alicyclic polyols such as diols having an alicyclic structure in the main chain, such as (ethyl)-1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, and 1,4-bis(hydroxyethoxy)cyclohexane; aromatic diols such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenedimethanol, and 3,4'-naphthalenedimethanol; polyester polyols of hydroxycarboxylic acids and diols, such as polyester polyols of 6-hydroxycaproic acid and hexanediol; polyester polyols of dicarboxylic acids and diols, such as polyester polyols of adipic acid and hexanediol; and polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, alicyclic polyols and / or aliphatic polyols are preferred, and aliphatic polyols are more preferred, from the viewpoints of improving the elongation and reducing the YI of the resin composition after curing and imparting a preferred viscosity to the resin composition. The polyol monomers may be used alone or in combination.As the alicyclic polyol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanediol are more preferred, and 1,4-cyclohexanedimethanol is even more preferred. As the aliphatic polyol, a linear aliphatic diol is preferred, and 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred, and 1,5-pentanediol and / or 1,6-hexanediol are even more preferred.

[0055] The carbonate ester is not particularly limited, and examples thereof include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate; aromatic carbonate esters such as diphenyl carbonate; and cyclic carbonate esters such as ethylene carbonate. In addition, phosgene or the like capable of producing polycarbonate polyol can also be used. Among these, aliphatic carbonate esters are preferred, and dimethyl carbonate is more preferred, in view of the ease of producing polycarbonate polyol.

[0056] The polycarbonate polyol (C) in the present invention is a polycarbonate polyol represented by the formula: [In the formula, R Ｘ is, in each occurrence, independently a divalent hydrocarbon group having 2 to 30 carbon atoms, and p is, for each repeating structural unit, independently an integer of 1 to 100.] and the total number of hydroxy groups at the molecular chain terminals (number of terminal hydroxy groups) is preferably 2 or more.

[0057] R Ｘ is independently in each occurrence a divalent hydrocarbon group of 2 to 30 carbon atoms.

[0058] R Ｘ is preferably, each occurrence independently, a linear divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms, a branched divalent aliphatic hydrocarbon group having 4 to 10 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group having 6 to 10 carbon atoms.

[0059] R Ｘ may be linear or branched. Ｘmay be a substituted or unsubstituted alkylene group. Ｘ When R is a substituted alkylene group, it is preferable that it does not contain a reactive group. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 3 to 10. Ｘ Examples of the alkyl group include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a 2,2-dimethylpropylene group, a 2-methylbutylene group, a 3-methylbutylene group, a 3-methyl-2-butylene group, a pentylene group, a 2-pentylene group, a 3-pentylene group, a 3-dimethyl-2-butylene group, a 3,3-dimethylbutylene group, a 3 , 3-dimethyl-2-butylene group, 2-ethylbutylene group, n-hexylene group, 2-hexylene group, 3-hexylene group, 2-methylpentylene group, 2-methyl-2-pentylene group, 2-methyl-3-pentylene group, 3-methylpentylene group, 3-methyl-2-pentylene group, 3-methyl-3-pentylene group, 4-methylpentylene group, 4-methyl-2-pentylene group, 2,2-dimethyl-3 -pentylene group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl-2-pentylene group, 3-ethyl-3-pentylene group, n-heptylene group, 2-heptylene group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6- Examples include a methyl-2-heptylene group, a 4-methyl-3-heptylene group, an octylene group, a 2-octylene group, a 3-octylene group, a 2-propylpentylene group, a 2,4,4-trimethylpentylene group, a decaoctylene group, a 1,3-cyclopentyl group, a 1,4-cyclohexyl group, a 1,5-cyclooctyl group, a 1,4-cyclohexanedimethylene group, and a 1,3-cyclohexanedimethylene group.

[0060] R in one repeating unit represented by formula (C1) Ｘ The group may be directly or indirectly bonded to another repeating structural unit represented by formula (C1).

[0061] Examples of the terminal group of the repeating structural unit represented by formula (C1) include a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, with a hydrogen atom being preferred.

[0062] p is an integer of 1 to 100, independently for each repeating structural unit.

[0063] The range of p may be an integer from 1 to 100, for example, 1 to 3, 1 to 5, 1 to 8, 1 to 10, 1 to 20, 1 to 50, 1 to 80, 2 to 5, 2 to 10, 2 to 15, 2 to 20, 2 to 30, 2 to 50, 2 to 100, 3 to 5, 3 to 10, 3 to 30, 3 to 50, 3 to 100, 5 to 10, 5 to 20, 5 to 30, 5 to 50, 5 to 100, etc.

[0064] The polycarbonate polyol (C) has one or more repeating structural units represented by formula (C1).

[0065] The number of such repeating structural units is not particularly limited, and may be, for example, 1 or more, 2 or more, 3 or more, 5 or more, 10 or more, 20 or more, or 30 or more. Also, it may be, for example, 100 or less, 75 or less, 50 or less, 30 or less, 20 or less, 10 or less, or 5 or less. In one embodiment, the number of repeating structural units is 1 to 2.

[0066] The structure of the portion linking the repeating units is not particularly limited, but in a preferred embodiment, the structure of such a portion may be a structure derived from the fact that the polycarbonate polyol (C) of the present invention is a reaction product of a polyhydric alcohol and phosgene, a reaction product of a polyhydric alcohol and a dialkyl carbonate, a reaction product of a polyhydric alcohol and a diaryl carbonate, or a ring-opening polymerization product of a polyhydric alcohol and a cyclic carbonate.

[0067] The polyhydric alcohol is not particularly limited, but examples thereof include ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), and sugar alcohols (such as xylitol and sorbitol).

[0068] The cyclic carbonate ester is not particularly limited, but examples thereof include trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

[0069] The polycarbonate polyol (C) is a compound having two or more terminal hydroxyl groups.

[0070] The polycarbonate polyol (C) has a structure in which a hydroxy group derived from the polyhydric alcohol starting material is present at each end of the molecular chain. In other words, as the branching increases, the number of hydroxy groups at the terminals of the polycarbonate polyol (C) (number of terminal hydroxyl groups) increases. The number of terminal hydroxyl groups is not particularly limited as long as it is 2 or more, but is preferably 2.

[0071] (Method for measuring the number of terminal hydroxyl groups) In the present invention, the number of terminal hydroxyl groups of the polycarbonate polyol is １ It can be calculated by H-NMR analysis. The specific procedure is as follows: (i) Polycarbonate polyol １ In the H-NMR spectrum, the molar ratio (H) of terminal OH calculated from the peaks derived from groups (e.g., methylene groups) bonded to the terminal hydroxy groups of the polycarbonate polyol, and the molar ratio (T) of polyfunctional polyol calculated from the peaks derived from the polyfunctional polyol structure are calculated; (ii) the value of 2+2T / (H−T) is the number of terminal hydroxyl groups.

[0072] The molar ratio (H) of terminal OH calculated from the peak derived from the group bonded to the terminal hydroxy group is obtained by dividing the integral value of the group bonded to the terminal hydroxy group by its number of protons. For example, when the group bonded to the terminal hydroxy group is a methylene group, it is obtained by dividing the integral value of the methylene group by the number of protons, 2. The molar ratio (T) of polyfunctional polyol calculated from the peak derived from the polyfunctional polyol structure is obtained by dividing the integral value of a peak derived from the polyfunctional polyol structure by its number of protons. For example, when a methylene group is used as the peak derived from the polyfunctional polyol structure, it is obtained by dividing the integral value of the methylene group by the number of protons, 2.

[0073] In the present invention, the number of terminal hydroxyl groups of a polycarbonate polyol is a numerical value determined by the above-mentioned measurement method and calculation formula. Since the numerical value obtained by the above-mentioned method may be an average value of the numbers of terminal hydroxyl groups of a plurality of polycarbonate polyol molecules, the number of terminal hydroxyl groups may not be an integer.

[0074] In a preferred embodiment, the polycarbonate polyol (C) has the following formula: [In the formula, R Ｙ are each independently an alkylene group having 2 to 30 carbon atoms in each occurrence, q is an integer of 1 to 100, and both terminals of the molecule are hydroxy groups.

[0075] R Ｙ is independently in each occurrence a hydrocarbon group having from 2 to 30 carbon atoms.

[0076] R Ｙ Examples of R Ｘ Examples of the hydrocarbon groups include those exemplified in the description of the above.

[0077] In a preferred embodiment, R Ｙ is a divalent linear aliphatic hydrocarbon group having 4 to 8 carbon atoms, a divalent branched aliphatic hydrocarbon group having 4 to 10 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group having 6 to 10 carbon atoms.

[0078] Examples of the linear divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms include an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, and an n-octylene group.

[0079] Examples of the divalent branched aliphatic hydrocarbon group having 4 to 10 carbon atoms include, but are not limited to, a 2-butylene group, a 2-hexylene group, a 3-hexylene group, a 2-octylene group, a 4-octylene group, a 6-methyl-2-heptylene group, a 2,2-dimethyl-3-pentylene group, and a 2,3-dimethyl-3-pentylene group.

[0080] Examples of divalent alicyclic hydrocarbon groups having 6 to 10 carbon atoms include, but are not limited to, 1,3-cyclopentyl, 1,4-cyclohexyl, and 1,5-cyclooctyl groups.

[0081] R in one repeating unit represented by formula (C2) Ｙ The group may be directly or indirectly bonded to another repeating structural unit represented by formula (C2).

[0082] Examples of the terminal group of the repeating structural unit represented by formula (C2) include a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, with a hydrogen atom being preferred.

[0083] q is an integer from 1 to 100.

[0084] The range of q may be an integer of 1 to 100, for example, 1 to 3, 1 to 5, 1 to 8, 1 to 10, 1 to 20, 1 to 50, 1 to 80, 2 to 5, 2 to 10, 2 to 15, 2 to 20, 2 to 30, 2 to 50, 2 to 100, 3 to 5, 3 to 10, 3 to 30, 3 to 50, 3 to 100, 5 to 10, 5 to 20, 5 to 30, 5 to 50, 5 to 100, etc.

[0085] In the present invention, the number average molecular weight (Mn) of the polycarbonate polyol (C) is not particularly limited, but in consideration of ease of synthesis, ease of handling, etc., it is preferably 350 to 10,000, further preferably 400 to 8,000, even more preferably 450 to 6,000, and particularly preferably 500 to 5,000.

[0086] The content of the polycarbonate polyol (C) is not particularly limited, and may be, for example, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 12% by mass or more, or 15% by mass or more, relative to the total mass of the resin composition of the present invention. Furthermore, the content of the polycarbonate polyol (C) may be, for example, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, relative to the total mass of the resin composition of the present invention. The content of the polycarbonate polyol (C) may be 0.5 to 60% by mass, preferably 1 to 40% by mass, and more preferably 1 to 25% by mass, relative to the total mass of the resin composition of the present invention.

[0087] The resin composition of the present invention may contain various additives other than the components described above, as necessary. Examples of such additives include an acid generator, a sensitizer, an epoxy group-containing compound, a radically polymerizable compound, and a radical polymerization initiator.

[0088] <Acid Generator> The resin composition of the present invention preferably contains an acid generator. In the present invention, the acid generator can be any compound or composition that can serve as a source of acid that serves as an initiator for cationic polymerization of the monofunctional oxetane compound (A), the aromatic bisoxetane compound (B), the epoxy group-containing compound (D), and other cationically polymerizable organic compounds. Among these, photoacid generators that can release acid when irradiated with active energy rays such as ultraviolet rays are preferred, and onium salts that can release protons are particularly preferred.

[0089] Such onium salts are not particularly limited, but examples thereof include oxonium salts, ammonium salts, phosphonium salts, sulfonium salts, and iodonium salts. Specific examples include triphenylsulfonium hexafluoroantimonate, triphenylphenacylphosphonium tetrafluoroborate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, thiodi-p-phenylenebis(diphenylsulfonium)bis(hexafluoroantimonate), diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, thiodi-p-phenylenebis(diphenylsulfonium)bis(hexafluorophosphate), diphenyl[4-(phenylsulfanyl)phenyl]sulfonium=trifluoro[tris(pentafluoroethyl)]λ(5)-phosphanide, (4-isopropylphenyl)(4-tolyl)iodonium=trifluoro[tris(pentafluoroethyl)]-λ(5)-phosphanide, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate. In the present invention, only one of the above-mentioned acid generators may be used, or two or more of them may be used.

[0090] The content of the acid generator in the composition of the present invention is not particularly limited, and may be, for example, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, or 5% by mass or more, relative to the total amount of the composition, and may be, for example, 15% by mass or less, 10% by mass or less, 7% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass or less, relative to the total amount of the composition.

[0091] <Sensitizer> For the purpose of promoting the above-mentioned polymerization reaction, the resin composition of the present invention may contain, if necessary, a photosensitizer such as pyrene, perylene, acridine orange, benzophenone, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, benzoin alkyl ether, thioxanthone, 1-chloro-4-propoxy-9H-thioxanthone-9-one, or 2-chlorothioxanthone, together with the cationic polymerization initiator.

[0092] <Epoxy Group-Containing Compound (D)> The resin composition of the present invention preferably further contains an epoxy group-containing compound (D), because the inclusion of an epoxy group-containing compound further increases the rate of the cationic polymerization reaction, making it easier to achieve a desired curing rate in the curing step of the resin composition.

[0093] As the epoxy group-containing compound (D), any compound preferably used as a cationically polymerizable organic compound can be used as long as it contains an epoxy group. Such epoxy group-containing compounds are not particularly limited, but examples thereof include alicyclic epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds. Specific examples of the epoxy group-containing compound (D) that can be used include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, diglycidyl ether of hydrogenated bisphenol A, and diglycidyl ether of bisphenol A.

[0094] In the present invention, the alicyclic epoxy compound refers to a compound having an alicyclic epoxy group, that is, a compound having an epoxy group in which one oxygen atom is added to the C═C double bond of an unsaturated aliphatic ring (for example, cyclohexene). Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, and dicyclohexylmethyl. Examples of epoxy compounds include 3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexane carboxylate, 2,2-bis(hydroxymethyl)-1-butanol, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct, 2,2-bis(hydroxymethyl)-1-butanol, 2,4-epoxycyclohexylmethane, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,1-bis(3,4-epoxycyclohexyl)ethane, alpha-pinene oxide, limonene monoxide, limonene dioxide, 4-vinylcyclohexene monoxide, 4-vinylcyclohexene dioxide, and 2,3'-bi(7-oxabicyclo[4,1,0]heptane).

[0095] Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, etc. More specific examples include diglycidyl ethers of hydrogenated bisphenol A, diglycidyl ethers of hydrogenated bisphenol F, diglycidyl ethers of 1,4-butanediol, diglycidyl ethers of 1,6-hexanediol, triglycidyl ethers of glycerin, triglycidyl ethers of trimethylolpropane, tetraglycidyl ethers of sorbitol, hexaglycidyl ethers of dipentaerythritol, diglycidyl ethers of polyethylene glycol, diglycidyl ethers of polypropylene glycol, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids. In addition to the above compounds, other examples include monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy butyl stearate, epoxy octyl stearate, epoxidized linseed oil, and epoxidized polybutadiene.

[0096] Examples of the aromatic epoxy compound include mono- or polyglycidyl ethers of monohydric or polyhydric phenols having at least one aromatic ring or alkylene oxide adducts thereof. Specific examples include glycidyl ethers obtained by reacting bisphenol A, bisphenol F, or alkylene oxide adducts thereof with epichlorohydrin, and monoglycidyl ethers of epoxy novolac resins, phenol, cresol, butylphenol, or polyether alcohols obtained by adding alkylene oxides to these.

[0097] The resin composition of the present invention may contain one or more of the above-mentioned epoxy group-containing compounds, if necessary. In one embodiment, the resin composition of the present invention contains an alicyclic epoxy compound and / or an aliphatic epoxy compound, or an alicyclic epoxy compound and / or an aromatic epoxy compound.

[0098] The content of the epoxy group-containing compound (D) in the resin composition of the present invention is not particularly limited, and may be, for example, 1 mass% or more, 5 mass% or more, 15 mass% or more, 30 mass% or more, 40 mass% or more, or 50 mass% or more, relative to the total amount of the composition. Furthermore, the content of the epoxy group-containing compound may be, for example, 80 mass% or less, 60 mass% or less, 40 mass% or less, 35 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less, relative to the total amount of the composition. The content of the epoxy group-containing compound (D) may be 1 to 60 mass%, preferably 5 to 50 mass%, and more preferably 5 to 35 mass%, relative to the total mass of the resin composition of the present invention.

[0099] <Radical Polymerizable Compound> The resin composition of the present invention preferably contains a radical polymerizable compound for the purpose of stabilizing the shape of the cured product. In this specification, the radical polymerizable compound refers to a compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with active energy rays in the presence of a radical polymerization initiator, and any compound such as a radical polymerizable resin, a monofunctional monomer having radical polymerizability, or a polyfunctional monomer can be used. The resin composition of the present invention may contain only one type of such radical polymerizable compound, or may contain two or more types.

[0100] In a preferred embodiment, the resin composition of the present invention contains a (meth)acrylic acid ester (E). The (meth)acrylic acid ester (E) can function as a radically polymerizable compound.

[0101] Such (meth)acrylic acid esters are not particularly limited, and may be either monofunctional (meth)acrylic acid esters or polyfunctional (meth)acrylic acid esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, stearyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, and isodecyl (meth)acrylate. acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, lauryl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, isobornyl (meth)acrylate, stearyl α-chloro (meth)acrylate, icosyl α-chloro (meth)acrylate, behenyl α-chloro (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedioic acid Examples of the acrylic acid esters include bisphenol A diglycidyl ether di(meth)acrylate, tripropylene glycol di(meth)acrylate, stearamidoethyl (meth)acrylate, 2-stearamidoethyl (meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, tris-(2-acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate.

[0102] The content of the (meth)acrylic acid ester in the resin composition of the present invention is not particularly limited, and may be, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, relative to the total amount of the composition. Furthermore, the content of the (meth)acrylic acid ester may be, for example, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to the total amount of the composition. The content of the (meth)acrylic acid ester (E) may be 1 to 50% by mass, preferably 5 to 40% by mass, and more preferably 10 to 30% by mass, relative to the total mass of the resin composition of the present invention.

[0103] <Radical Polymerization Initiator> When the resin composition of the present invention contains a radical polymerizable compound, it is preferable that the resin composition contain a radical polymerization initiator. In the present invention, any polymerization initiator that can initiate radical polymerization of a radical polymerizable compound when irradiated with active energy rays can be used as the radical polymerization initiator. Examples of the radical polymerization initiator include aromatic ketone compounds such as benzil or its dialkyl acetal compounds, phenyl ketone compounds, acetophenone compounds, benzoin or its alkyl ether compounds, benzophenone compounds, phosphine oxide compounds, and thioxanthone compounds.

[0104] Specific examples of benzil or its dialkyl acetal compounds that can be used as radical polymerization initiators include benzil dimethyl ketal, benzyl-β-methoxyethyl acetal, etc. Specific examples of phenyl ketone compounds include 1-hydroxy-cyclohexyl phenyl ketone, etc. Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, and 1,1'-[methylenebis(4,1-phenylene)]bis(2-methyl-2-hydroxy-1-propanone).

[0105] Examples of benzoin compounds that can be used as radical polymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, benzoin isobutyl ether, etc. Examples of benzophenone compounds that can be used as radical polymerization initiators include benzophenone, 4-methylbenzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,-4'-dichlorobenzophenone, etc.

[0106] Examples of phosphine oxide compounds that can be used as radical polymerization initiators include phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, etc. Examples of thioxanthone compounds that can be used as radical polymerization initiators include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

[0107] In the present invention, one or more of the above-mentioned radical polymerization initiators can be used. Among them, 1-hydroxycyclohexyl phenyl ketone is preferably used as the radical polymerization initiator because the resulting cured product has a good hue (low yellowness, etc.).

[0108] The resin composition of the present invention may contain various additives as other optional components as necessary, as long as they do not inhibit the curing of the present invention. Examples of such additives include water, solvents, pigments, colorants, antifoaming agents, fillers (polymer particles, silica, glass powder, ceramic powder, metal powder, etc.), leveling agents, surfactants, thickeners, plasticizers, UV absorbers, polymerization inhibitors, antioxidants, and bases.

[0109] The resin composition of the present invention may have a viscosity of, for example, 50 mPa·s or more, 100 mPa·s or more, 150 mPa·s or more, 190 mPa·s or more, 230 mPa·s or more, or 250 mPa·s or more. The resin composition of the present invention may have a viscosity of, for example, 1000 mPa·s or less, 700 mPa·s or less, 450 mPa·s or less, 400 mPa·s or less, 350 mPa·s or less, or 330 mPa·s or less. The resin composition of the present invention may have a viscosity of, for example, 50 to 1000 mPa·s, 100 to 700 mPa·s, 150 to 450 mPa·s, or 190 to 400 mPa·s.

[0110] The viscosity can be measured using an E-type viscometer (manufactured by BROOKFIELD) after adjusting the temperature of the resin composition to 25°C.

[0111] The resin composition of the present invention can be prepared by mixing the above-mentioned compounds and additives under any conditions and by any method.

[0112] In one aspect, the resin composition of the present invention is used for a 3D printer and can be suitably used by a stereolithography 3D printer.

[0113] Curing the resin composition may involve depositing multiple layers of the resin composition onto the substrate prior to irradiation, at least one of which is a resin composition according to the present invention.

[0114] The illuminated portions can be patterned through the use of a photomask, by direct write application of light, by interference, nanoimprint, or diffractive gradient lithography, by inkjet 3D printing, stereolithography, holography, LCD, or digital light projection (DLP).

[0115] The resin composition may be irradiated by any of a wide variety of methods known in the art. Patterning may be achieved by photolithography using positive or negative image photomasks, interference lithography (i.e., using diffraction gratings), near-field nanopatterning by diffraction gradient lithography, or direct laser writing application of light, such as multiphoton lithography, nanoimprint lithography, inkjet 3D printing, stereolithography, and digital micromirror array variations of stereolithography (commonly referred to as digital light projection (DLP)). The resin composition is particularly suitable for preparing structures using stereolithography methods, including digital light projection (DLP). The resin composition may also be processed as a bulk structure, for example, using vat polymerization, where the photopolymer is cured directly onto a translated or rotated substrate, and irradiation is patterned via stereolithography, holography, or digital light projection (DLP).

[0116] Stereolithography (SLA) is a form of three-dimensional (3D) printing technology used to create models, prototypes, patterns, production parts, etc., layer-by-layer (so-called "additive manufacturing") using photopolymerization (a process in which light bonds molecular chains to form polymers). These polymers then compose a three-dimensional solid body. Typically, an SLA additive manufacturing process uses a build platform with a build tray immersed in a liquid photosensitive material. A 3D model of the item to be manufactured is imported into the associated 3D printer software. The software slices the 3D model into a 2D image, which is projected onto the build platform to expose the photopolymer.

[0117] [Cured Resin Product] The present invention provides a cured resin product obtained by curing the resin composition of the present invention.

[0118] For example, when the resin composition of the present invention is used as a resin material for a stereolithography 3D printer, a cured resin product that overcomes the problems of the present invention can be obtained.

[0119] The tensile elongation of the cured resin product of the present invention is measured in accordance with JIS K7127. This tensile elongation may preferably be 10% or more, 13% or more, 15% or more, or 18% or more. The tensile elongation of the cured resin product of the present invention may be, for example, 50% or less, or 45% or less. In this application, "measured in accordance with JIS K7127" means that the measurement is performed in accordance with the procedure described in the JIS standard. The details other than the procedure, particularly the shape and dimensions of the test specimen, are not limited to those listed in the JIS standard. For example, in this specification, the test specimen used in the tensile test was rectangular, measuring 110 mm long, 1.5 mm wide, and 1.0 mm thick.

[0120] The tensile modulus of the cured resin of the present invention may preferably be 1.0 GPa or more, 1.2 GPa or more, or 1.3 GPa or more, and may be, for example, 2.0 GPa or less.

[0121] The tensile stress of the cured resin material of the present invention may be preferably 30 MPa or more, 40 MPa or more, or 50 MPa or more, and may be, for example, 100 MPa or less.

[0122] The YI (yellow index) of the cured resin product of the present invention indicates the degree of yellowness. The YI of the cured resin product of the present invention is a value measured at a thickness of 1.0 mm, and the measurement method is as described below. The YI of the cured resin product of the present invention may preferably be 10 or less, 8 or less, 5 or less, or 3 or less. The YI of the cured resin product of the present invention may also be, for example, 0.01 or more.

[0123] In a preferred embodiment, the cured resin of the present invention has a tensile elongation of 10% or more, 13% or more, 15% or more, or 18% or more, and a YI of 10 or less, 8 or less, 5 or less, or 3 or less.

[0124] The haze of the cured resin product of the present invention is a measurement value at a thickness of 1.0 mm, and the measurement method is as described below. The haze of the cured resin product of the present invention may be preferably 10% or less, 7% or less, 5% or less, or 3% or less. The haze of the cured resin product of the present invention may be, for example, 0.01% or more.

[0125] <Method for Producing Cured Resin Product> The cured resin product of the present invention is produced by curing the resin composition of the present invention. Here, in this specification, "curing" refers to copolymerizing the monofunctional oxetane compound (A), the aromatic bisoxetane compound (B), and the epoxy group-containing compound (if contained in the resin composition) in the resin composition by cationic polymerization.

[0126] The cationic polymerization method includes a method in which cationic species, which are active species, are generated by heating or irradiation with active energy rays, and the method using irradiation with active energy rays is particularly preferred.

[0127] The active energy rays irradiated to the resin composition of the present invention are not particularly limited, and examples thereof include ultraviolet rays, electron beams, X-rays, radioactive rays, and high-frequency waves. From an economical viewpoint, ultraviolet rays having a wavelength of 300 to 410 nm are preferably used. In this case, examples of the light source that can be used include ultraviolet lasers (e.g., semiconductor-pumped solid-state lasers, Ar lasers, He—Cd lasers, etc.), high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light-emitting diodes), and ultraviolet fluorescent lamps.

[0128] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0129] Examples of the present invention will be specifically described below, but unless otherwise specified in the specification, the examples do not limit the present invention.

[0130] The test methods used below are as follows:

[0131] Viscosity The resin compositions described in the following Examples or Comparative Examples were placed in a thermostatic bath at 25°C, and the temperature of the resin compositions was adjusted to 25°C. Thereafter, the viscosity of the resin compositions was measured using an E-type viscometer (manufactured by BROOKFIELD).

[0132] Tensile Test The tensile stress, tensile modulus, and tensile elongation at break (tensile elongation) of the cured resin products described in the following Examples or Comparative Examples were measured in accordance with JIS K 7127. Detailed dimensions are as described in the following Examples or Comparative Examples, respectively.

[0133] YI The yellowness index (YI) of the cured resin products (thickness: 1.0 mm) described in the following Examples and Comparative Examples was measured using a microsurface spectrocolorimeter (ZE6000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0134] Haze The haze of the cured resin products (thickness: 1.0 mm) described in the following Examples or Comparative Examples was measured using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0135] Raw materials used in the following examples and comparative examples are shown below. Unless otherwise specified, the molecular weights shown below are number average molecular weights. 3-Ethyl-3-hydroxymethyloxetane (ETERNACOLL (registered trademark) EHO, manufactured by UBE Corporation) 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl (ETERNACOLL (registered trademark) OXBP, manufactured by UBE Corporation) 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate (Celloxide (registered trademark) 2021P, manufactured by Daicel Corporation) Diglycidyl ether of hydrogenated bisphenol A (Denacol (registered trademark) EX-252, manufactured by Nagase ChemteX Corporation) Diglycidyl ether of bisphenol A (jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation) Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) Polytetramethylene glycol diacrylate (A-PTMG65, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polycarbonate diol (ETERNACOLL (registered trademark) PH-100, molecular weight 1000, number of terminal hydroxyl groups 2.0, manufactured by UBE Corporation) Polycarbonate diol (ETERNACOLL (registered trademark) PH-50, molecular weight 500, number of terminal hydroxyl groups 2.0, manufactured by UBE Corporation) Polycarbonate diol (ETERNACOLL (registered trademark) PH-200, molecular weight 2000, number of terminal hydroxyl groups 2.0, manufactured by UBE Corporation) Polycarbonate diol (ETERNACOLL (registered trademark) UH-100, molecular weight 1000, number of terminal hydroxyl groups 2.0, manufactured by UBE Corporation) Polycarbonate polyol (UBE Fine Chemicals Polycarbonate diol (manufactured by UBE Fine Chemicals Asia, HPCP-200, molecular weight 2000, number of terminal hydroxyl groups 7.1) Polycarbonate diol (manufactured by UBE Corporation, ETERNACOLL (registered trademark) UHC50-100, molecular weight 1000, number of terminal hydroxyl groups 2.0) Polycarbonate diol (manufactured by UBE Corporation, ETERNACOLL (registered trademark) UM90 (1 / 3), molecular weight 900, number of terminal hydroxyl groups 2.0) Polycarbonate triol (manufactured by UBE Fine Chemicals Asia, UF-100, molecular weight 1000, number of terminal hydroxyl groups 3.0)・A 50:50 mass% mixture of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate and propylene carbonate (CPI (registered trademark)-101A, manufactured by San-Apro Co., Ltd.) ・A mixture of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate and thiodi-p-phenylenebis(diphenylsulfonium)bis(hexafluoroantimonate) (T201S, manufactured by Tronly) ・1-hydroxy-cyclohexyl phenyl ketone (Irgacure (registered trademark) 184, manufactured by IGM Resins B.V.)

[0136] Preparation of Resin Compositions The resin compositions of the Examples and Comparative Examples were prepared by placing the raw materials in a container according to the description of each Example or Comparative Example in Table 1 and stirring at room temperature until homogenous. The values ​​in Table 1 are parts by weight.

[0137] Curing of Resin Composition In the following Examples and Comparative Examples, cured resin compositions were prepared as follows.

[0138] The resin composition was placed in a space created by a glass plate, a PET film, and a silicone rubber mold, and a UV-LED (manufactured by HOYA) with a wavelength of 365 nm was irradiated at 20 mW / cm. ２ The coating was then left to stand at a temperature of 23° C. and a humidity of 50% for 1 day to obtain a cured resin.

[0139] Example 1 20 parts by weight of 3-ethyl-3-hydroxymethyloxetane, 20 parts by weight of 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 40 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 20 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of polycarbonate diol (PH-100, manufactured by UBE Co., Ltd., molecular weight 1000, number of terminal hydroxyl groups 2.0), 4.0 parts by weight of a 50:50 mass% mixture of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate and propylene carbonate (CPI (registered trademark)-101A, manufactured by San-Apro Co., Ltd.), and a radical polymerization initiator (1-hydroxycyclohexylphenyl ketone). A resin composition was prepared by stirring 2.0 parts by weight of acrylic acid and 1.2 parts by weight of water at room temperature until homogeneous. The viscosity of the resin composition was measured. A cured resin measuring 110 mm x 1.5 mm x 1.0 mm was prepared from the resulting resin composition and subjected to a tensile test. Furthermore, the YI and haze of a 1.0 mm-thick cured resin were measured.

[0140] Examples 2 to 16 and Comparative Examples 1 to 11 For the other examples and comparative examples, resin compositions and cured resins were prepared using the blending ratios of raw materials shown in Table 1, and various physical properties were measured. The resin compositions and cured resins were prepared using the same procedures as in Example 1. The results of each measurement are shown in Table 2 or Table 3. In Table 2, "mass %" indicates the ratio of the mass of the constituent component to the total mass of the resin composition.

[0141] Evaluation of cured resin Examples in which the tensile elongation at break (elongation) of the cured resin was 10% or more and the YI was 10 or less were evaluated as "OK," while Comparative Examples in which the above conditions were not met were evaluated as "NG." The evaluation results are shown in Table 2.

[0142]

[0143]

[0144]

[0145] Comparison of Examples and Comparative Examples 1, 2, 3, 4, 9, 10, and 11 revealed that when the resin composition contains all of the monofunctional oxetane compound (A), the aromatic bisoxetane compound (B), and the polycarbonate polyol (C) (condition A), a resin composition having high elongation and low yellowness after curing can be obtained. Comparison of Examples 1, 7, 8, and 9 and Comparative Examples 5 to 8 revealed that under condition A, when the content of the polycarbonate polyol (C) is 1 to 25 mass% relative to the total mass of the resin composition, a resin composition having even lower yellowness after curing can be obtained. Examples 1 to 16 revealed that even when various polycarbonate polyols (C) are used, resin compositions having high elongation and low yellowness after curing can be obtained.

[0146] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0147] According to the present invention, it is possible to provide a resin composition having high elongation after curing and low yellowness. The resin composition of the present invention can be used in a wide range of applications, for example, in 3D printer applications.

Claims

1. A resin composition comprising a monofunctional oxetane compound (A), an aromatic bisoxetane compound (B), and a polycarbonate polyol (C), wherein the content of the polycarbonate polyol (C) is 1 to 25 mass% relative to the total mass of the resin composition.

2. The resin composition according to claim 1, which is for use in a 3D printer.

3. The resin composition according to claim 1, wherein the aromatic bisoxetane compound (B) comprises 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl.

4. The resin composition according to claim 1, wherein the content of the aromatic bisoxetane compound (B) is 1 to 50 mass % based on the total mass of the resin composition.

5. The resin composition according to claim 1, which contains an acid generator.

6. The polycarbonate polyol (C) is represented by the following formula: [In the formula, R Ｘ and each occurrence of p is independently a divalent hydrocarbon group having 2 to 30 carbon atoms, and p is independently an integer of 1 to 100 for each repeating structural unit.

7. In formula (C1), R Ｘ and each occurrence is independently a linear divalent aliphatic hydrocarbon group having 4 to 8 carbon atoms, a branched divalent aliphatic hydrocarbon group having 4 to 10 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group having 6 to 10 carbon atoms.

8. The resin composition according to claim 1, further comprising an epoxy group-containing compound (D).

9. The resin composition according to claim 8, wherein the epoxy group-containing compound (D) has an alicyclic structure.

10. The resin composition according to claim 1, further comprising a (meth)acrylic acid ester (E).

11. The resin composition according to claim 1, having a viscosity of 50 to 1,000 mPa·s.

12. A cured resin obtained by curing the resin composition according to any one of claims 1 to 11.

13. The cured resin product according to claim 12, which has a tensile elongation of 10% or more as measured in accordance with JIS K7127 and a YI of 10 or less at a thickness of 1.0 mm.

14. The cured resin product according to claim 13, having a haze of 10% or less at a thickness of 1.0 mm.

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