Resin composition

Abstract

Provided is a resin composition containing: a polycarbonate polyol (A) in which the number of terminal hydroxyl groups is greater than 2; and an epoxy group–containing compound (B) and / or an oxetane compound (C). 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, a photocurable resin composition containing an oxetane compound has been disclosed as a method for producing shaped objects with high productivity by shortening the exposure time to active energy rays, which has high curing sensitivity to active energy rays.

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

[0004] However, the cured product of the resin composition has insufficient elongation, and therefore has the drawback of being brittle and easily broken when used in a stereolithography 3D printer. Furthermore, when the compounding recipe is changed to eliminate this drawback, the haze of the cured product tends to worsen, and therefore, when the resin composition is used in a stereolithography 3D printer, there is also the drawback that 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 haze after curing.

[0006] The present invention includes the following aspects: [Item 1] A resin composition comprising a polycarbonate polyol (A) having more than two terminal hydroxyl groups, and an epoxy group-containing compound (B) and / or an oxetane compound (C). [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 epoxy group-containing compound (C) has an alicyclic structure. [Item 4] The resin composition according to any one of Items 1 to 3, wherein the polycarbonate polyol (A) has 2.1 to 10 terminal hydroxyl groups. [Item 5] The resin composition according to any one of Items 1 to 4, wherein the oxetane compound (C) is at least one selected from the group consisting of 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 3-ethyl-3-hydroxymethyloxetane, 3,3'-(oxybis(methylene))bis(3-ethyloxetane), 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane, 3-ethyl-3-(allyloxymethyl)oxetane, bis[(3-ethyl-3-oxetanyl)methyl]isophthalate, (3-ethyl-3-oxetanyl)methyl methacrylate, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, and 2-ethylhexyloxetane. [Item 6] The resin composition according to any one of Items 1 to 5, wherein the total content of the epoxy group-containing compound (B) and the oxetane compound (C) is 1 to 90% by mass, based on the total mass of the resin composition. [Item 7] The resin composition according to any one of Items 1 to 6, wherein the content of the polycarbonate polyol (A) is 1 to 50% by mass, based on the total mass of the resin composition. [Item 8] The resin composition according to any one of Items 1 to 7, further comprising an acid generator. [Item 9] The resin composition according to any one of Items 1 to 8, further comprising a (meth)acrylic acid ester. [Item 10] The resin composition according to any one of Items 1 to 9, having a viscosity of 50 to 1000 mPa s. [Item 11] A cured resin product obtained by curing the resin composition according to any one of Items 1 to 10. [Item 12] The cured resin product according to Item 11, wherein the ratio of tensile elongation to haze at a thickness of 1.0 mm (tensile elongation (%) / haze (%)) measured according to JIS K7127 is 8.0 or more.[Item 13] The cured resin product according to Item 12, having a YI of 5 or less at a thickness of 1.0 mm.

[0007] The present invention can provide a resin composition that has high elongation and low haze 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 hydroxy group, an amino group, a carboxylic acid group, a sulfonic acid group, a phosphate group, an alkali metal or alkaline earth metal base of a carboxylic acid, sulfonic acid, or phosphate, an ammonium base with a counter anion of chlorine, bromine, or iodine ion, and other ionic groups.

[0011] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

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

[0013] The composition contains a polycarbonate polyol (A) having more than two terminal hydroxyl groups, and an epoxy group-containing compound (B) and / or an oxetane compound (C).

[0014] In one embodiment, the resin composition of the present invention is particularly suitable for use in 3D printers.

[0015] <Polycarbonate polyol (A) having more than two terminal hydroxyl groups>

[0016] The polycarbonate polyol (A) in the present invention has a total number of hydroxy groups (hydroxyl groups) at molecular chain terminals (number of terminal hydroxyl groups) of more than 2.

[0017] The polycarbonate polyol (A) can be obtained by reacting one or more polyol components 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, as they are easy to produce and do not produce chlorinated terminal compounds as by-products.

[0018] 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 haze 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.

[0019] 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.

[0020] Since the polycarbonate polyol (A) has a total number of hydroxyl groups at the molecular chain terminals (number of terminal hydroxyl groups) greater than 2, the precursor monomer for the polycarbonate polyol contains a polyhydric alcohol. A polyhydric alcohol is a compound having three or more hydroxyl groups in one molecule. Examples of polyhydric alcohols include compounds such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol. These may be used alone or in combination of two or more.

[0021] (Molar Ratio of Diol to Polyhydric Alcohol) The amounts (molar ratio) of the aliphatic diol and polyhydric alcohol used are not particularly limited as long as the total number of hydroxy groups at the molecular chain terminals (number of terminal hydroxyl groups) is greater than 2, but is preferably 0.3 to 4.0 in terms of "total number of moles of hydroxyl groups in polyhydric alcohol / total number of moles of hydroxyl groups in aliphatic diol." As an example, the molar ratio of the aliphatic diol to the polyhydric alcohol can be determined by completely hydrolyzing the polycarbonate polyol (A) and identifying and quantifying the aliphatic diol and polyhydric alcohol by means of gas chromatography, mass spectrometry, NMR measurement, or the like. When other diol compounds, such as diols having an alicyclic structure, are used in addition to the aliphatic diol, the molar ratio of the total amount of diol compounds used to the amount of polyhydric alcohol used is also calculated in the same manner as above, and is preferably 0.3 to 4.0.

[0022] In a preferred embodiment, the polycarbonate polyol (A) has the following formula: [In the formula, R Ｘ is independently in each occurrence a divalent hydrocarbon group having 2 to 30 carbon atoms, and p is independently in each repeating structural unit an integer of 1 to 100. and the number of terminal hydroxyl groups is greater than two.

[0023] R Ｘ is independently in each occurrence a divalent hydrocarbon group having 2 to 30 carbon atoms.

[0024] 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.

[0025] R Ｘ may be linear or branched. Ｘ may be a substituted or unsubstituted alkylene group. ＸWhen 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, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a 2,2-dimethylpropylene group, a 2-methylbutylene group, a 2-methyl-2-butylene 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, a 2-ethylbutylene group, a hexylene group, a 2-hexylene group, a 3-hexylene group, a 2-methylpentylene group, a 2-methyl-2-pentylene group, a 2-methyl-3-pentylene group, a 3-methylpentylene group, a 3-methyl-2-pentylene group, a 3-methyl-3-pentylene group, Examples thereof include an ethylene group, a 4-methylpentylene group, a 4-methyl-2-pentylene group, a 2,2-dimethyl-3-pentylene group, a 2,3-dimethyl-3-pentylene group, a 2,4-dimethyl-3-pentylene group, a 4,4-dimethyl-2-pentylene group, a 3-ethyl-3-pentylene group, a heptylene group, a 2-heptylene group, a 3-heptylene group, a 2-methyl-2-hexylene group, a 2-methyl-3-hexylene group, a 5-methylhexylene group, a 5-methyl-2-hexylene group, a 2-ethylhexylene group, a 6-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, and a decaoctylene group.

[0026] R in one repeating unit represented by formula (A1) Ｘ The group may be directly or indirectly bonded to another repeating structural unit represented by formula (A1).

[0027] Examples of the terminal group of the repeating structural unit represented by formula (A1) include a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, with a hydrogen atom being preferred.

[0028] p is an integer of 1 to 100, independently for each repeating structural unit.

[0029] 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.

[0030] The polycarbonate polyol (A) has two or more repeating structural units represented by formula (A1).

[0031] The number of such repeating structural units is not particularly limited, and may be, for example, 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, 5 or less, or 3 or less.

[0032] 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 (A) 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.

[0033] The cyclic carbonate ester is not particularly limited, but examples thereof include trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

[0034] The polycarbonate polyol (A) is a compound having more than two terminal hydroxyl groups.

[0035] Polycarbonate polyols having more than two terminal hydroxyl groups are generally hyperbranched polymers, and have a structure in which a hydroxy group derived from the polyhydric alcohol starting material is present at the end of each branched chain. In other words, as the degree of branching increases, the number of terminal hydroxy groups of the polycarbonate polyol (A) increases.

[0036] (Method for measuring the number of terminal hydroxyl groups) In the present invention, the number of terminal hydroxyl groups of the polycarbonate polyol is１ 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.

[0037] 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.

[0038] 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.

[0039] The number of terminal hydroxyl groups may be preferably 2.1 or more, 2.5 or more, 3.0 or more, 4.0 or more, or 6.0 or more. The number of terminal hydroxyl groups may be, for example, 10 or less, 9.0 or less, or 8.0 or less. The number of terminal hydroxyl groups is preferably 2.1 to 10, more preferably 2.5 to 9.0, and even more preferably 6.0 to 8.0.

[0040] In the present invention, the number average molecular weight (Mn) of the polycarbonate polyol (A) 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.

[0041] The content of the polycarbonate polyol (A) 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, 15% by mass or more, 20% by mass or more, or 25% by mass or more, relative to the total mass of the resin composition of the present invention. Furthermore, the content of the polycarbonate polyol (A) may be, for example, 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 (A) may be, for example, 0.5 to 60% by mass, preferably 1 to 50% by mass, and more preferably 1 to 40% by mass, relative to the total mass of the resin composition of the present invention.

[0042] <Epoxy Group-Containing Compound (B)> The resin composition of the present invention preferably contains an epoxy group-containing compound (B), because the inclusion of the epoxy group-containing compound improves the rate of cationic polymerization of the resin composition of the present invention, making it easier to achieve a desired curing rate in the curing step of the resin composition.

[0043] As the epoxy group-containing compound (B), any compound that contains an epoxy group and is preferably used as a cationically polymerizable organic compound can be used.

[0044] The epoxy group-containing compound (B) is not particularly limited, but examples thereof include epoxy compounds having an alicyclic structure, such as alicyclic epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds. Specifically, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, diglycidyl ether of hydrogenated bisphenol A, and diglycidyl ether of bisphenol A are preferred.

[0045] In the present invention, the alicyclic epoxy compound refers to a compound having an alicyclic epoxy group, that is, 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).

[0046] 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, examples of the epoxy resin 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.

[0047] 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.

[0048] 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.

[0049] The content of the epoxy group-containing compound (B) in the resin composition of the present invention is not particularly limited, and may be, for example, 0.5% by mass or more, 1% by mass or more, 5% by mass or more, 15% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, or 50% by mass or more, based on the total amount of the composition. Furthermore, the content of the epoxy group-containing compound (B) may be, for example, 80% by mass or less, 60% by mass or less, 40% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 3% by mass or less, based on the total amount of the composition. The content of the epoxy group-containing compound (B) in the resin composition of the present invention may be, for example, 0.5 to 80% by mass, preferably 1 to 70% by mass, and more preferably 10 to 60% by mass.

[0050] <Oxetane Compound (C)> The resin composition of the present invention preferably contains an oxetane compound (C). In particular, when the resin composition of the present invention contains both the epoxy group-containing compound (B) and the oxetane compound (C), a desired curing rate can be more easily achieved in the curing step of the resin composition.

[0051] In the present invention, the oxetane compound (C) is preferably a compound represented by the following formula: [In the formula, R ａ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ｂ is a monovalent organic group.

[0052] R ａ is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0053] 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 ａis an ethyl group.

[0054] R ｂ is a monovalent organic group.

[0055] The monovalent organic group may be any monovalent organic group as long as it allows the oxetane compound (C) to exist stably.

[0056] In one embodiment, R ｂ may have one or more of various functional groups and / or bonds. The type of such functional group is not particularly limited, but examples thereof 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 type of such bond is not particularly limited, but examples thereof include ether bonds, ester bonds, and amide bonds. In one embodiment, R ｂ has a hydroxy group. ｂ has an ether bond.

[0057] In a preferred embodiment, R ｂ is -CH ２ It's OH.

[0058] Examples of oxetane compounds (C) include those 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 organic group.]

[0059] R ｃ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0060] 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.

[0061] R ｄ is a divalent organic group.

[0062] The divalent organic group may be any divalent organic group as long as the oxetane compound (C2) can exist stably.

[0063] In a preferred embodiment, R ｄ is a divalent aromatic group having one or more aromatic rings. ｄ may have, for example, 1 to 6 aromatic rings. ｄ has 1 to 2 aromatic rings.

[0064] 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.

[0065] 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. In a preferred embodiment, R 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.

[0066] This R ｄ Examples of the 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) ｎ a 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 (C3), two R ２ may be bonded to any carbon atom on the benzene ring.

[0067] R １ are each independently an alkylene group having 1 to 6 carbon atoms.

[0068] R １ 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.

[0069] 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.

[0070] R ２The 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 unsubstituted. 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.

[0071] R ３ is independently in each occurrence an alkylene group of 2 to 5 carbon atoms.

[0072] R ３ The alkylene group having 1 to 6 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.

[0073] 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 (C3).

[0074] - (R ３ O) ｎ In the formula (I), n is an integer of 1 to 4, preferably an integer of 1 or 2.

[0075] R ２ Ga-(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.

[0076] R ４is a single bond or an alkylene group having 1 to 6 carbon atoms.

[0077] R ４ 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.

[0078] 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.

[0079] In formula (C3), 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.

[0080] R ｄ Other examples include 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.

[0081] R ５ is independently in each occurrence an alkylene group of 1 to 6 carbon atoms.

[0082] R ５ may be linear or branched. ５R may be a substituted or unsubstituted alkylene group, but is preferably an unsubstituted alkylene group. ５ 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. ５ is preferably a methylene group.

[0083] In formula (C4), m is an integer of 1 to 3. In formula (C4), m is more preferably 1.

[0084] Preferred specific examples of the oxetane compound (C) include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 3-ethyl-3-hydroxymethyloxetane, 3,3'-(oxybis(methylene))bis(3-ethyloxetane), 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane, 3-ethyl-3-(allyloxymethyl)oxetane, bis[(3-ethyl-3-oxetanyl)methyl]isophthalate, (3-ethyl-3-oxetanyl)methyl methacrylate, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, and 2-ethylhexyloxetane, and more preferred examples include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl and 3-ethyl-3-hydroxymethyloxetane.

[0085] The resin composition of the present invention may contain one or more of the above-mentioned oxetane compounds (C) as needed. In one embodiment, the resin composition of the present invention contains one oxetane compound (C).

[0086] The content of the oxetane compound (C) 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, 20% by mass or more, or 25% by mass or more, relative to the total mass of the resin composition of the present invention. Furthermore, the content of the oxetane compound (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, or 15% by mass or less, relative to the total mass of the resin composition of the present invention. The content of the oxetane compound (C) may be, for example, 0.5 to 60% by mass, preferably 1 to 40% by mass, and more preferably 5 to 30% by mass, relative to the total mass of the resin composition of the present invention.

[0087] The resin composition of the present invention contains an epoxy group-containing compound (B) and / or an oxetane compound (C). That is, the resin composition of the present invention may contain the epoxy group-containing compound (B) but not the oxetane compound (C). Alternatively, the resin composition may not contain the epoxy group-containing compound (B) but may contain the oxetane compound (C). Alternatively, the resin composition may contain both the epoxy group-containing compound (B) and the oxetane compound (C). In a preferred embodiment, the resin composition contains both the epoxy group-containing compound (B) and the oxetane compound (C). In another preferred embodiment, the resin composition contains the epoxy group-containing compound (B) but not the oxetane compound (C).

[0088] In the present invention, the total content of the epoxy group-containing compound (B) and the oxetane compound (C) is not particularly limited, and may be, for example, 0.5 mass% or more, 1 mass% or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, 40 mass% or more, 60 mass% or more, 70 mass% or more, or 80 mass% or more, relative to the total mass of the resin composition. Furthermore, the total content of the epoxy group-containing compound (B) and the oxetane compound (C) may be, for example, 95 mass% or less, 90 mass% or less, 70 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 10 mass% or less, or 5 mass% or less, relative to the total mass of the resin composition of the present invention. The total content of the epoxy group-containing compound (B) and the oxetane compound (C) is 0.5 to 95 mass%, preferably 1 to 90 mass%, more preferably 10 to 90 mass%, and even more preferably 30 to 80 mass%, relative to the resin composition of the present invention.

[0089] 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.

[0090] <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 epoxy group-containing compound (B), the oxetane compound (C), 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.

[0091] 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.

[0092] 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, 5% by mass or more, or 7% by mass or more, relative to the total amount of the composition. The content of the acid generator 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.

[0093] <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, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, benzophenone, benzoin alkyl ether, thioxanthone, 1-chloro-4-propoxy-9H-thioxanthone-9-one, or 2-chlorothioxanthone, together with the cationic polymerization initiator.

[0094] <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.

[0095] In a preferred embodiment, the resin composition of the present invention contains a (meth)acrylic acid ester. The (meth)acrylic acid ester (E) can function as a radical polymerizable compound.

[0096] 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.

[0097] 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 8 to 30% by mass, relative to the total mass of the resin composition of the present invention.

[0098] <Radical Polymerization Initiator> When the resin composition of the present invention contains the 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 the 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.

[0099] 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).

[0100] 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.

[0101] 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.

[0102] 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.).

[0103] 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 (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.), leveling agents, surfactants, thickeners, plasticizers, UV absorbers, polymerization inhibitors, antioxidants, etc.

[0104] 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.

[0105] The viscosity can be measured using an E-type viscometer (manufactured by BROOKFIELD) after adjusting the temperature of the resin composition to 25°C.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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).

[0110] 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).

[0111] 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.

[0112] [Cured Resin Product] The present invention provides a cured resin product obtained by curing the resin composition of the present invention.

[0113] 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.

[0114] 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 5% or more, 6% or more, 7% or more, 10% or more, or 20% or more. The tensile elongation of the cured resin product of the present invention may be, for example, 80% or less, or 60% 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.

[0115] The tensile modulus of the cured resin of the present invention may be preferably 0.5 GPa or more, 1.0 GPa or more, or 1.3 GPa or more, and may be, for example, 2.0 GPa or less.

[0116] The tensile stress of the cured resin product of the present invention may be preferably 20 MPa or more, 25 MPa or more, 30 MPa or more, or 40 MPa or more, and may be, for example, 100 MPa or less.

[0117] 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, 5 or less, 3 or less, or 2 or less. The YI of the cured resin product of the present invention may also be, for example, 0.01 or more.

[0118] 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, 5% or less, 4% or less, or 2% or less. The haze of the cured resin product of the present invention may be, for example, 0.01% or more.

[0119] The present invention can provide a resin composition that has high elongation and low haze after curing. That is, in a preferred embodiment, the cured resin product of the present invention has a large ratio of the tensile elongation (%) to the haze (%) (tensile elongation (%) / haze (%)), and specifically, this ratio is preferably 8 or greater, more preferably 10 or greater, and even more preferably 12 or greater.

[0120] <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. Herein, "curing" refers to (co)polymerizing the epoxy group-containing compound (B) and / or the oxetane compound (C) in the resin composition by cationic polymerization.

[0121] Examples of the cationic polymerization method include 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.

[0122] 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.

[0123] 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.

[0124] Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0125] The test methods used below are as follows:

[0126] 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).

[0127] 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.

[0128] 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.).

[0129] 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.).

[0130] 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) 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.) Trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polytetramethylene glycol diacrylate (A-PTMG65, manufactured by Shin-Nakamura Chemical Co., Ltd.) Polycarbonate diol (UBE Corporation) ETERNACOLL (registered trademark) PH-100, molecular weight 1000, number of terminal hydroxyl groups 2.0) Polycarbonate polyol (HPCP-200, manufactured by UBE Fine Chemicals Asia, molecular weight 2000, number of terminal hydroxyl groups 7.1) Polycarbonate triol (UF-100, manufactured by UBE Fine Chemicals Asia, 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.) Mixture of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate and thiodi-p-phenylenebis(diphenylsulfonium)bis(hexafluoroantimonate) (T201S, manufactured by Tronly) 1-hydroxy-cyclohexylphenyl ketone (Irgacure® 184, manufactured by IGM Resins B.V.)

[0131] Preparation of Resin Compositions The resin compositions of the Examples and Comparative Examples were prepared by placing raw materials in a container according to the values ​​shown in Table 1 and stirring at room temperature until homogenous. The values ​​in Table 1 are in parts by weight.

[0132] Curing of Resin Composition In the following Examples and Comparative Examples, cured resin compositions were prepared as follows.

[0133] 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.

[0134] Example 1 A resin composition was prepared by stirring 25 parts by weight of 3-ethyl-3-hydroxymethyloxetane, 50 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 25 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of polycarbonate polyol (HPCP-200, molecular weight 2000, number of terminal hydroxyl groups 7.1, manufactured by UBE Fine Chemicals Asia), 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.), 2.0 parts by weight of a radical polymerization initiator (1-hydroxy-cyclohexylphenyl ketone), and 1.2 parts by weight of water at room temperature until homogeneous. The viscosity of the resin composition was measured. A cured resin product measuring 110 mm x 1.5 mm x 1.0 mm was prepared from the resulting resin composition and subjected to a tensile test. The haze of the cured resin product having a thickness of 1.0 mm was also measured.

[0135] Examples 2 to 8 and Comparative Examples 1 to 6 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 measurement results are shown in Table 2 or Table 3.

[0136] Evaluation of cured resin products Examples in which the ratio of tensile elongation at break (elongation, %) to haze (%) of the cured resin product, i.e., (elongation / haze) was 8.0 or higher, were evaluated as "OK," while comparative examples that did not satisfy the above conditions were evaluated as "NG." The evaluation results are shown in Table 2. In Table 2, "mass %" indicates the ratio of the mass of a constituent component to the total mass of the resin composition.

[0137] Comparison of Examples and Comparative Examples 1 to 6 revealed that when the resin composition contains a polycarbonate polyol (A) having more than two terminal hydroxyl groups, an epoxy group-containing compound (B), and an oxetane compound (C), it is possible to obtain a resin composition that has high elongation and low haze after curing. Furthermore, it was found that when the resin composition contains a polycarbonate polyol (A) having more than two terminal hydroxyl groups, the resin composition has higher elongation and lower haze after curing than a resin composition containing only a polycarbonate polyol having two terminal hydroxyl groups.

[0138] 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.

[0139] According to the present invention, it is possible to provide a resin composition having high elongation and low haze after curing. 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 polycarbonate polyol (A) having more than two terminal hydroxyl groups, and an epoxy group-containing compound (B) and / or an oxetane compound (C).

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 epoxy group-containing compound (B) has an alicyclic structure.

4. The resin composition according to claim 1, wherein the polycarbonate polyol (A) has 2.1 to 10 terminal hydroxyl groups.

5. The resin composition according to claim 1, wherein the oxetane compound (C) is at least one selected from the group consisting of 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 3-ethyl-3-hydroxymethyloxetane, 3,3'-(oxybis(methylene))bis(3-ethyloxetane), 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane, 3-ethyl-3-(allyloxymethyl)oxetane, bis[(3-ethyl-3-oxetanyl)methyl]isophthalate, (3-ethyl-3-oxetanyl)methyl methacrylate, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, and 2-ethylhexyloxetane.

6. The resin composition according to claim 1, wherein the total content of the epoxy group-containing compound (B) and the oxetane compound (C) is 1 to 90 mass % based on the total mass of the resin composition.

7. The resin composition according to claim 1, wherein the content of the polycarbonate polyol (A) is 1 to 50 mass % based on the total mass of the resin composition.

8. The resin composition according to claim 1, further comprising an acid generator.

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

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

11. A cured resin obtained by curing the resin composition according to any one of claims 1 to 10.

12. The cured resin product according to claim 11, wherein the ratio of tensile elongation measured in accordance with JIS K7127 to haze at a thickness of 1.0 mm (tensile elongation (%) / haze (%)) is 8.0 or more.

13. The cured resin product according to claim 12, having a YI of 5 or less at a thickness of 1.0 mm.

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