Curable resin composition for white three-dimensional molded objects, method for producing white three-dimensional molded object, and white three-dimensional molded object

Abstract

To provide a curable resin composition for white three-dimensional molded objects that possesses various properties during photolithography while achieving plastic-like white appearance.SOLUTION: A curable resin composition for white three-dimensional molded objects comprises a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), and a one-end-capped polyalkylene oxide compound with a specific structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable resin composition for a white three-dimensional object, a method for producing a white three-dimensional object, and a white three-dimensional object. [Background technology]

[0002] Stereolithography is a technology that creates three-dimensional objects by applying active energy ray drawing to a curable resin composition based on three-dimensional CAD data. Stereolithography is widely adopted because it can produce the desired three-dimensional objects with good dimensional accuracy without creating a mold or the like.

[0003] Three-dimensional objects obtained by optical three-dimensional modeling using a resin composition for optical three-dimensional modeling are widely used as models for verifying the appearance design of various industrial products during the design process, models for checking the functionality of parts, resin molds for producing casting molds, base models for producing metal molds, etc. In recent years, there has been a demand for objects that can be used in fields where general-purpose plastics are used, such as building materials such as exterior wall materials, housings for lighting and the like, mock-up models for home appliance prototypes, design presentation models for buildings, high-definition design models, etc.

[0004] As photocurable resin compositions for stereolithography, various curable resin compositions have been proposed, such as a curable resin composition containing a radically polymerizable organic compound, a curable resin composition containing a cationically polymerizable organic compound, and a curable resin composition containing both a radically polymerizable organic compound and a cationically polymerizable organic compound.

[0005] Radical polymerizable organic compounds such as (meth)acrylate-based compounds have drawbacks in terms of dimensional stability, since oxygen inhibition occurs, resulting in insufficient curing on the surface of the shaped object, and the resin shrinks during curing. In order to overcome such drawbacks, curable resin compositions containing both radical polymerizable organic compounds and cationically polymerizable organic compounds have been developed. However, when a photocurable resin composition containing an epoxy compound is used as a cationic polymerizable organic compound, a photo-modeled object having excellent dimensional accuracy can be obtained, but the object has a drawback that it has poor impact resistance and is prone to cracking. In order to compensate for the drawbacks of the epoxy compound, a method of blending rubber particles or a method of adding a polyalkylene ether have been proposed.

[0006] For example, a resin composition for optical 3D modeling containing specific amounts of a specific radical polymerizable organic compound, a specific cationic polymerizable organic compound, an active energy ray-sensitive radical polymerization initiator, and an active energy ray-sensitive cationic polymerization initiator (Patent Document 1), and a resin composition for optical 3D modeling containing a cationic polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator, and a radical polymerization initiator (Patent Document 2) have been reported. In addition, a photocurable composition containing a specific epoxy-containing compound, a multifunctional (meth)acrylate, a mixture containing two specific polyols, a cationic photoinitiator, and a free radical photoinitiator has been reported (Patent Document 3). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2010-174104 A [Patent Document 2] JP 2018-053133 A [Patent Document 3] International Publication No. 2007 / 031505 Summary of the Invention [Problem to be solved by the invention]

[0008] When a model obtained by stereolithography is to be used as an actual part in a field where general-purpose plastics are used, the model is required to have physical properties and an appearance that allow it to be used directly as an actual part. The resin composition for stereolithography described above has various properties such as high resolution of the model, excellent modeling accuracy, and small volumetric shrinkage during curing, and is excellent in mechanical properties such as impact resistance, but is still insufficient in terms of the texture of plastics, such as white appearance. In addition, if a white pigment or rubber particles is added, a cured product with a white appearance can be obtained, but there is a problem that the white solid of the added pigment etc. settles, and even if it does not settle, the liquid resin becomes opaque, making it difficult to handle, and there is also a problem that any defects are not known until the modeling is completed.

[0009] The objects molded from the resin compositions of Patent Documents 1 and 2 have excellent transparency but are inferior in the plastic-like white appearance. In Patent Document 3, a mixture containing two specific polyols is used to obtain a molded object having an opaque white appearance like ABS resin. However, in reality, the degree of whiteness cannot be determined without trying out different blending ratios of the mixture containing the two specific polyols, making it difficult to obtain the desired white molded object as planned.

[0010] Therefore, an object of the present invention is to provide a curable resin composition for a white three-dimensional object, which has various properties for stereolithography and achieves a plastic-like white appearance. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to achieve the above object, and as a result, have found that the above-mentioned problems can be solved by preparing a resin composition containing a polyalkylene oxide compound, one end of which is capped with a specific group, together with a cationically polymerizable organic compound (A) and a radically polymerizable organic compound (B), and have thus completed the present invention.

[0012] The gist of the present invention is as follows. [1] A curable resin composition for white three-dimensional objects, comprising a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), and a one-end-capped polyalkylene oxide compound represented by formula (I). [ka] [In the formula, R 1 and R 2 may be the same or different and each independently represents at least one selected from alkylene groups having 2 to 8 carbon atoms, m represents an integer of 20 to 200, n represents an integer of 0 to 100, and X represents at least one selected from alkyl groups having 1 to 8 carbon atoms. [2] The curable resin composition for a white three-dimensional object according to the above [1], wherein the one-end-capped polyalkylene oxide compound represented by the formula (I) has a number average molecular weight of 500 to 20,000. [3] The curable resin composition for a white three-dimensional object according to the above [1] or [2], wherein the cationically polymerizable organic compound (A) is a compound having an epoxy group. [4] The curable resin composition for a white three-dimensional object according to the above [1] or [2], wherein the radical polymerizable organic compound (B) is a compound having a (meth)acrylic group. [5] The curable resin composition for a white three-dimensional object according to the above [1] or [2], further comprising an oxetane compound. [6] The curable resin composition for a white three-dimensional object according to the above [1] or [2], which contains 1 to 30 mass % of the one-end-capped polyalkylene oxide compound represented by the formula (I). [7] A method for producing a white three-dimensional object by irradiating the curable resin composition for a white three-dimensional object according to the above item [1] or [2] with active energy rays. [8] A white three-dimensional object obtained by curing the curable resin composition for a white three-dimensional object according to [1] or [2] above. Effect of the Invention

[0013] According to the present invention, it is possible to provide a curable resin composition for a white three-dimensional object, which has various properties during stereolithography and achieves a plastic-like white appearance, a method for producing a white three-dimensional object, and a white three-dimensional object. In addition, a white three-dimensional object molded using the curable resin composition of the present invention is excellent in mechanical properties such as sliding properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] An example of an embodiment of the present invention will be described in detail below. However, the present invention is not limited to the embodiment described below, and can be modified as desired without departing from the gist of the present invention.

[0015] The curable resin composition for a white three-dimensional object of the present invention (hereinafter, sometimes simply referred to as "curable resin composition of the present invention") can be cured into a predetermined shape by irradiating it with active energy rays. For example, the white three-dimensional object of the present invention can be produced by irradiating the curable resin composition for a white three-dimensional object with active energy rays to cure the resin to a predetermined thickness, supplying one layer of liquid resin on the cured layer, and then irradiating it with active energy rays in the same manner to cure it, and repeating the lamination operation to obtain such a cured layer.

[0016] <One-end-capped polyalkylene oxide compound> The curable resin composition of the present invention is characterized by containing a one-end-capped polyalkylene oxide compound represented by the following formula (I). [ka] [In the formula, R 1 and R 2 may be the same or different and each independently represents at least one selected from alkylene groups having 2 to 8 carbon atoms, m represents an integer of 20 to 200, n represents an integer of 0 to 100, and X represents at least one selected from alkyl groups having 1 to 8 carbon atoms.

[0017] Above R 1 and R 2The alkylene group having 2 to 8 carbon atoms may be linear or branched. Specific examples of the alkylene group having 2 to 8 carbon atoms include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group (tetramethylene group), an isobutylene group, a tert-butylene group, a linear or branched pentylene group [e.g., -CH2CH2CH2CH2CH2-, -CH2H2CH(CH3)CH2-, etc.], a linear or branched hexylene group [e.g., -CH2CH2CH2CH2CH2-, -CH2CH2CH(CH3)CH2CH2-, -CH2CH2CH(C2H5)CH2-, etc.], a heptylene group, and an octylene group. If the number of carbon atoms is 1, the growth of the domain described below becomes insufficient, making it difficult to obtain effects such as a white appearance, and it is also chemically unstable, which is not preferable. If the carbon number exceeds 8, compatibility is poor, making it difficult to obtain the desired effect. Among them, R 1 and R 2 are preferably each independently selected from the group consisting of an n-propylene group, an isopropylene group, an n-butylene group (tetramethylene group), an n-pentylene group, a branched pentylene group represented by the formula: -CH2CH2CH(CH3)CH2-, an n-hexylene group, and a branched hexylene group represented by the formula: -CH2CH2CH(CH3)CH2CH2- or -CH2CH2CH(C2H5)CH2-, and are more preferably selected from an n-propylene group, an isopropylene group, and an n-butylene group (tetramethylene group).

[0018] The one-end-capped polyalkylene oxide compound represented by the above formula (I) may be a homopolymer compound or a copolymer compound. For example, R 1 and R 2 When are the same or when n is 0, the one-end-capped polyalkylene oxide compound represented by formula (I) is a homopolymer compound. When the one-end-capped polyalkylene oxide compound represented by the above formula (I) is a copolymer compound, it may be either a block copolymer or a random copolymer.

[0019] In the above formula (I), m is preferably 20 to 150, more preferably 30 to 130, even more preferably 40 to 100, still more preferably 45 to 100, and even more preferably 50 to 95. In the above formula (I), n can be adjusted in accordance with the desired molecular weight and the above m, and is preferably 0 to 80, more preferably 0 to 50, even more preferably 0 to 45, and even more preferably 0 to 40. When m and n in formula (I) are within the above ranges, the molecular weight of the one-end-capped polyalkylene oxide can be adjusted to a desired range.

[0020] X in formula (I) is at least one selected from alkyl groups having 1 to 8 carbon atoms. When such a one-end-capped polyalkylene oxide compound is contained in the curable resin composition of the present invention, the obtained shaped product exhibits a plastic-like white appearance and also has excellent sliding properties. Without being bound by a specific theory, the following mechanism is considered to be one of the reasons why such an effect is exhibited. The reaction of the radical polymerizable organic compound (B) contained in the curable resin composition of the present invention is completed quickly, while the polymerization of the cationic polymerizable organic compound (A) proceeds relatively slowly. The hydroxyl group of the one-end-capped polyalkylene oxide compound represented by formula (I) attacks the active end during the polymerization of this cationic polymerizable organic compound (A), and it is incorporated into the cured resin that forms the matrix, and it is believed that the polyalkylene oxide chains incorporated into the matrix cured resin are entangled with each other to form a domain. At this time, it is believed that the polyalkylene oxide chain with one end capped grows larger, has a large light scattering ability, exhibits a white appearance, and the proportion of the grown domain on the surface of the cured product is also high, so that the sliding property is also high.

[0021] The number of carbon atoms in the alkyl group represented by X is 1 to 8, as described above, preferably 1 to 6, more preferably 2 to 6, and even more preferably 2 to 4. If the number of carbon atoms in the alkyl group represented by X exceeds 8, the foaming property of the polyalkylene oxide compound increases, which leads to problems such as a decrease in handleability, a negative effect on aesthetics such as bubbles remaining on the molded product due to the generation of bubbles during the molding operation, and a decrease in mechanical properties (such as impact strength and tensile strength) due to bubbles being trapped. Therefore, it becomes necessary to take measures such as slowing down the molding operation speed to suppress the generation of bubbles and breaking the generated bubbles, which is industrially disadvantageous. If both terminal hydroxyl groups of the polyalkylene oxide compound are blocked, there will be no active terminals for polymerization, making it impossible for the compound to perform the desired function.

[0022] The number average molecular weight of the one-end-capped polyalkylene oxide compound represented by the above formula (I) is preferably 500 to 20,000, more preferably 500 to 15,000, even more preferably 500 to 10,000, still more preferably 800 to 8,000, and even more preferably 1,000 to 8,000. When the number average molecular weight is 500 or more, a shaped product having high whiteness and excellent sliding properties can be obtained, and when it is 20,000 or less, compatibility with other resins contained in the resin composition is excellent and the viscosity of the resin composition can be appropriately maintained. In this specification, the number average molecular weight of the polyalkylene ether compound refers to a number average molecular weight measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0023] The content of the one-end-capped polyalkylene oxide compound represented by the above formula (I) in the curable resin composition of the present invention is preferably 1 to 30 mass%, more preferably 1 to 25 mass%, even more preferably 3 to 25 mass%, and even more preferably 5 to 20 mass% based on the mass of the curable resin composition. If the content of the one-end-capped polyalkylene ether compound is 1 mass% or more, domains are effectively formed, and a shaped product having high whiteness and sliding properties can be obtained. On the other hand, if it is 30 mass% or less, there is no adverse effect on the mechanical properties such as tensile strength and hardness of the shaped product, or heat resistance.

[0024] <Cationically polymerizable organic compound (A)> The cationic polymerizable organic compound may be a compound that undergoes polymerization and / or crosslinking when irradiated with active energy rays in the presence of an active energy ray-sensitive cationic polymerization initiator.Typical examples include epoxy compounds, cyclic ether compounds, cyclic acetal compounds, cyclic lactone compounds, cyclic thioether compounds, spiro orthoester compounds, and vinyl ether compounds.The cationic polymerizable organic compound may be used alone or in the form of a mixture of two or more.

[0025] Specific examples of the cationically polymerizable organic compound (A) include the following. (1) Epoxy compounds such as alicyclic epoxy resins, aliphatic epoxy resins, and aromatic epoxy resins; (2) oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-methyl-3-phenoxymethyloxetane, and 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene; oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; and cyclic ether or cyclic acetal compounds such as trioxane, 1,3-dioxolane, and 1,3,6-trioxanecyclooctane; (3) Cyclic lactone compounds such as β-propiolactone and ε-caprolactone; (4) Thiirane compounds such as ethylene sulfide and thioepichlorohydrin; (5) Thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthietane; (6) Vinyl ether compounds such as ethylene glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), and triethylene glycol divinyl ether; (7) spiro ortho ester compounds obtained by reacting epoxy compounds with lactones; (8) Ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene, and polybutadiene.

[0026] Among the above, it is preferable to use at least an epoxy compound as the cationically polymerizable organic compound (A), and specifically, it is more preferable to use a polyepoxy compound having two or more epoxy groups in one molecule. In particular, it is preferable to use an epoxy compound (mixture of epoxy compounds) containing an alicyclic polyepoxy compound having two or more epoxy groups in one molecule and the content of the alicyclic polyepoxy compound is 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the epoxy compounds, as the cationic polymerizable organic compound. By using such a cationic polymerizable organic compound, the cationic polymerization rate, thick film curing property, resolution, active energy ray permeability, etc. when producing a white three-dimensional object are further improved, and the viscosity of the curable resin composition is lowered to allow smooth shaping, and the volume shrinkage rate of the obtained three-dimensional object is further reduced.

[0027] Examples of the alicyclic epoxy resin include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, and cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidizing cyclohexene or cyclopentene ring-containing compounds with a suitable oxidizing agent such as hydrogen peroxide or peracid. More specifically, examples of the alicyclic epoxy resin include hydrogenated bisphenol A monoglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane ... 4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, and the like.

[0028] Examples of the aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. More specific examples of the diglycidyl ether include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, diglycidyl ether of polytetramethylene 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-mentioned epoxy compounds, examples of the epoxy compounds 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.

[0029] Examples of the aromatic epoxy resin include mono- or polyglycidyl ethers of monohydric or polyhydric phenols having at least one aromatic nucleus or their alkylene oxide adducts.Specific examples include glycidyl ethers obtained by reacting bisphenol A, bisphenol AD, bisphenol Z, bisphenol F, or their alkylene oxide adducts with epichlorohydrin, glycidyl ethers obtained by reacting trisphenols or tetrakisphenols such as 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane or 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane with epichlorohydrin, and monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to epoxy novolac resins, phenols, cresols, butylphenols, or these.

[0030] <Radical polymerizable organic compound (B)> As the radical polymerizable organic compound, any compound that undergoes polymerization reaction and / or crosslinking reaction when irradiated with active energy rays in the presence of an active energy ray sensitive radical polymerization initiator can be used.Typical examples of such compounds include compounds with (meth)acrylate groups, unsaturated polyester compounds, aryl urethane compounds, polythiol compounds, etc., and one or more of the above-mentioned radical polymerizable organic compounds can be used. Among them, compounds having at least one (meth)acrylic group in one molecule are preferably used. Specific examples include reaction products of epoxy compounds and (meth)acrylic acid, (meth)acrylic acid esters of alcohols, urethane (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, etc.

[0031] The reaction product of the epoxy compound and (meth)acrylic acid may be (meth)acrylate-based reaction products obtained by reacting aromatic epoxy compounds, alicyclic epoxy compounds and / or aliphatic epoxy compounds with (meth)acrylic acid. Among (meth)acrylate-based reaction products, (meth)acrylate-based reaction products obtained by reacting aromatic epoxy compounds with (meth)acrylic acid are preferably used, and specific examples include (meth)acrylate obtained by reacting glycidyl ether obtained by reacting bisphenol compounds such as bisphenol A and bisphenol S or their alkylene oxide adducts with epoxidizing agents such as epichlorohydrin with (meth)acrylic acid, and (meth)acrylate-based reaction products obtained by reacting epoxy novolac resin with (meth)acrylic acid.

[0032] Examples of the (meth)acrylic acid esters of the above alcohols include (meth)acrylates obtained by reacting aromatic alcohols, aliphatic alcohols, alicyclic alcohols, and / or their alkylene oxide adducts, each of which has at least one hydroxyl group in the molecule, with (meth)acrylic acid. More specifically, for example, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isooctyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,Polyalkylene glycol mono(meth)acrylates such as 6-hexanediol di(meth)acrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monoacrylate, and polytetramethylene glycol monomethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, diacrylates of poly(oxyethylene / oxypropylene random copolymer) diol, dimethacrylates of poly(oxyethylene / oxypropylene random copolymer) diol, diacrylates or dimethacrylates of block copolymers (block copolymer diols) in which polyoxyethylene polymer blocks / polyoxypropylene polymer blocks are bonded and have hydroxyl groups at both ends, polytetramethylene glycol Examples of the polyalkylene glycol di(meth)acrylate include diacrylates or dimethacrylates of random copolymer diols in which ethylene oxide units and tetramethylene oxide units are randomly bonded and have hydroxyl groups at both ends, diacrylates or dimethacrylates of block copolymers (block copolymer diols) in which polyoxyethylene polymer blocks / polytetramethylene glycol polymer blocks are bonded and have hydroxyl groups at both ends, dipentaerythritol poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, tricyclodecane dimethanol diacrylate, and (meth)acrylates of alkylene oxide adducts of polyhydric alcohols such as the above-mentioned diols, triols, tetraols, and hexaols. As the (meth)acrylate of an alcohol, a (meth)acrylate having two or more (meth)acrylic groups in one molecule obtained by reacting a polyhydric alcohol with (meth)acrylic acid is preferably used. Among the (meth)acrylate compounds, acrylate compounds are more preferably used than methacrylate compounds in terms of polymerization rate.

[0033] Specific examples of polyalkylene glycol mono(meth)acrylates that can be used in the present invention include, but are not limited to, "Blenmer AE90" manufactured by Nippon Oil & Fats Co., Ltd. (number of ethylene oxide units ≒ 2, Monoacrylate of polyethylene glycol having an average molecular weight of about 90); "Blenmer AE200" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polyethylene glycol with an average molecular weight of about 200 and a bond number of ethylene oxide units of approximately 4.5); - "Blenmer AE400" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polyethylene glycol with an average molecular weight of about 400 and a bond number of ethylene oxide units of about 10); - "Blenmer PE90" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polyethylene glycol with an average molecular weight of about 90 and an ethylene oxide unit bond number of ≒2); - "Blenmer PE200" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polyethylene glycol with an average molecular weight of about 200 and a bond number of ethylene oxide units of ≒4.5); - "Blenmer PE350" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polyethylene glycol with an average molecular weight of about 350 and an ethylene oxide unit bond number of ≒8); "Blenmer AP150" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polypropylene glycol with propylene oxide unit bond number ≒ 3 and average molecular weight of about 150); "Blenmer AP250" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polypropylene glycol with a bond number of propylene oxide units of approximately 4 and an average molecular weight of approximately 250); - "Blenmer AP400" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polypropylene glycol with propylene oxide unit bond number ≒ 6 and average molecular weight of about 400); "Blenmer AP550" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polypropylene glycol with propylene oxide unit bond number ≒ 9 and average molecular weight of about 550); "Blenmer AP800" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polypropylene glycol with propylene oxide unit bond number ≒ 13 and average molecular weight of about 800); - "Blenmer PP500" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polypropylene glycol with propylene oxide unit bond number ≒ 9 and average molecular weight of about 500); "Blenmer PP800" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polypropylene glycol with propylene oxide unit bond number ≒ 13 and average molecular weight of about 800); Some examples include:

[0034] Further specific examples of polyalkylene glycol mono(meth)acrylates that can be used in the present invention include: - "Blenmer 10AEP550B" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polyethylene glycol / polypropylene glycol with ethylene oxide unit bond number ≒ 1, propylene oxide unit bond number ≒ 9, average molecular weight of about 550); "BLEMMER 10PEP550B" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polyethylene glycol polypropylene glycol with ethylene oxide unit bond number ≒ 1, propylene oxide unit bond number ≒ 9, average molecular weight of about 550); "Blenmer 55PET400" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polyethylene glycol tetramethylene glycol with ethylene oxide unit bond number ≒ 5, tetramethylene glycol unit bond number ≒ 3, and average molecular weight of about 400); "Blenmer 55AET800" manufactured by Nippon Oil & Fats Co., Ltd. (monoacrylate of polyethylene glycol tetramethylene glycol with ethylene oxide unit bond number ≒ 10, tetramethylene glycol unit bond number ≒ 5, average molecular weight ≒ 800); "Blenmer 55PET800" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polyethylene glycol tetramethylene glycol with ethylene oxide unit bond number ≒ 10, tetramethylene glycol unit bond number ≒ 5, and average molecular weight of about 800); "Blenmer 30PPT800" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polypropylene glycol and tetramethylene glycol with a bond number of propylene oxide units ≒ 4, a bond number of tetramethylene glycol units ≒ 8, and an average molecular weight of about 800); "Blenmer 50APT800" manufactured by Yushi Corporation (polypropylene glycol tetramethylene glycol monoacrylate with propylene oxide unit bond number ≒ 7, tetramethylene glycol unit bond number ≒ 5.5, and average molecular weight of about 800); "Blenmer 50PPT800" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polypropylene glycol and tetramethylene glycol with a bond number of propylene oxide units ≒ 7, a bond number of tetramethylene glycol units ≒ 5.5, and an average molecular weight of about 800); "Blenmer 70PPT800" manufactured by Nippon Oil & Fats Co., Ltd. (monomethacrylate of polypropylene glycol and tetramethylene glycol with a bond number of propylene oxide units ≒ 10, bond number of tetramethylene glycol units ≒ 3, and average molecular weight of about 800); Some examples include:

[0035] Among the polyalkylene glycol di(meth)acrylates that can be used in the present invention, specific examples of the polyethylene glycol di(meth)acrylate include, but are not limited to, the following: *NOF Corporation "Blenmar ADE-200", Shin-Nakamura Chemical Co., Ltd. "A-200", Kyoeisha Chemical Co., Ltd. "Light Acrylate 4EG-A" (all of these are polyethylene glycol diacrylates with ethylene oxide unit bond number ≒ 4 and average molecular weight ≒ 300); *NOF Corporation "Blenmar ADE-400", Shin-Nakamura Chemical Co., Ltd. "A-400", Kyoeisha Chemical Co., Ltd. "Light Acrylate 9EG-A", Hitachi Chemical Co., Ltd. "FA-240A" (all of these are polyethylene glycol diacrylates with ethylene oxide unit bond number ≒ 9 and average molecular weight ≒ 500); * Shin-Nakamura Chemical Co., Ltd. "A-600" (polyethylene glycol diacrylate with ethylene oxide unit bond number ≒ 14 and average molecular weight ≒ 750); * Shin-Nakamura Chemical Co., Ltd. "A-1000" (polyethylene glycol diacrylate with ethylene oxide unit bond number ≒ 23 and average molecular weight ≒ 1100); *NOF Corporation "Blenmar DPE-200", Shin-Nakamura Chemical Co., Ltd. "4G", Hitachi Chemical Co., Ltd. "FA-220M" (all of these are polyethylene glycol dimethacrylates with ethylene oxide unit bond number ≒ 4 and average molecular weight ≒ 330); *NOF Corporation's "Blenmar DPE-400" and Shin-Nakamura Chemical Co., Ltd.'s "9G" (both are polyethylene glycol dimethacrylates with ethylene oxide unit bond number ≒ 9 and average molecular weight ≒ 530-540); *NOF Corporation's "Blenmer DPE-600" (polyethylene glycol dimethacrylate with ethylene oxide unit bond number ≒ 13 and average molecular weight ≒ 690); *"14G" manufactured by Shin-Nakamura Chemical Co., Ltd. (Polyethylene glycol dimethacrylate with ethylene oxide unit bond number ≒ 14 and average molecular weight ≒ 740); *"23G" manufactured by Shin-Nakamura Chemical Co., Ltd. (Polyethylene glycol dimethacrylate with ethylene oxide unit bond number ≒ 23 and average molecular weight ≒ 1140); Some examples include:

[0036] Specific examples of polypropylene glycol di(meth)acrylate that can be used in the present invention include: *"APG-200" manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol diacrylate with propylene oxide unit bond number ≒ 3 and average molecular weight ≒ 300); *NOF Corporation's "Blenmer ADP-200" (polypropylene glycol dimethacrylate with propylene oxide unit bond number ≒ 4 and average molecular weight ≒ 360); *"APG-400" manufactured by Shin-Nakamura Chemical Co., Ltd., and "FA-P240A" manufactured by Hitachi Chemical Co., Ltd. (both are polypropylene glycol diacrylates with a bond number of propylene oxide units of approximately 7 and an average molecular weight of approximately 530 to 540); *NOF Corporation's "Blenmer ADP-400" (polypropylene glycol dimethacrylate with propylene oxide unit bond number ≒ 9 and average molecular weight ≒ 650); * Hitachi Chemical Co., Ltd.'s "FA-P270A" (polypropylene glycol diacrylate with propylene oxide unit bond number ≒ 12 and average molecular weight ≒ 820); *"APG-700" manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol diacrylate with propylene oxide unit bond number ≒ 12 and average molecular weight ≒ 810); *"9PG" manufactured by Shin-Nakamura Chemical Co., Ltd. (polypropylene glycol dimethacrylate with propylene oxide unit bond number ≒ 7 and average molecular weight ≒ 540); *NOF Corporation's "Blenmer PDP-400" (polypropylene glycol dimethacrylate with propylene oxide unit bond number ≒ 9 and average molecular weight ≒ 680); Some examples include:

[0037] Specific examples of polytetramethylene glycol di(meth)acrylate that can be used in the present invention include: *"A-PTMG-65" manufactured by Shin-Nakamura Chemical Co., Ltd. (Polytetramethylene glycol diacrylate with tetramethylene oxide unit bond number ≒ 9 and average molecular weight ≒ 750); * "FA-PTG9A" manufactured by Hitachi Chemical Co., Ltd. (polytetramethylene glycol diacrylate with tetramethylene oxide unit bond number ≒ 9 and average molecular weight ≒ 770); *"A-PTMG-100" manufactured by Shin-Nakamura Chemical Co., Ltd. (Polytetramethylene glycol diacrylate with tetramethylene oxide unit bond number ≒ 14 and average molecular weight ≒ 1130); *NOF Corporation's "Blenmer PDT-800" (polytetramethylene glycol dimethacrylate with tetramethylene oxide unit bond number ≒ 11, average molecular weight ≒ 920); Some examples include:

[0038] Specific examples of other polyalkylene glycol di(meth)acrylates that can be used in the present invention include NOF Corporation's "Blenmer PDET" (dimethacrylate of poly(oxyethylene / oxypropylene) block copolymer diol), "Blenmer ADET" (diacrylate of poly(oxyethylene / oxypropylene) block copolymer diol), "Blenmer PDPT" (dimethacrylate of poly(oxypropylene / oxytetramethylene) copolymer diol), "Blenmer ADPT" (diacrylate of poly(oxypropylene / oxytetramethylene) block copolymer diol), "Blenmer PDC" (dimethacrylate of poly(oxyethylene / oxypropylene / oxyethylene) copolymer diol), and "Blenmer ADC" (diacrylate of poly(oxyethylene / oxypropylene / oxyethylene) block copolymer diol).

[0039] Among the polyalkylene glycol di(meth)acrylates listed above, polyethylene glycol diacrylate, polypropylene glycol diacrylate, and polytetramethylene glycol diacrylate are preferably used because they are liquid at room temperature and therefore easy to handle, are easily available, have high reactivity, and can rapidly produce a three-dimensional object, etc. Among them, using polytetramethylene glycol diacrylate alone or using polytetramethylene glycol diacrylate in combination with either or both of polyethylene glycol diacrylate and polypropylene glycol diacrylate is more preferable because the physical properties such as toughness of the stereolithography object are further improved.

[0040] The urethane (meth)acrylate may be, for example, a (meth)acrylate obtained by reacting a hydroxyl group-containing (meth)acrylic acid ester with an isocyanate compound. The hydroxyl group-containing (meth)acrylic acid ester is preferably a hydroxyl group-containing (meth)acrylic acid ester obtained by esterification reaction of an aliphatic dihydric alcohol with (meth)acrylic acid, and a specific example thereof may be 2-hydroxyethyl (meth)acrylate. The isocyanate compound is preferably a polyisocyanate compound having two or more isocyanate groups in one molecule, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.

[0041] The polyester (meth)acrylate may be, for example, a polyester (meth)acrylate obtained by reacting a hydroxyl group-containing polyester with (meth)acrylic acid. The above-mentioned polyether (meth)acrylate may be a polyether acrylate obtained by reacting a hydroxyl-containing polyether with acrylic acid.

[0042] In the curable resin composition of the present invention, as the cationically polymerizable organic compound (A) and the radically polymerizable organic compound (B), one or more of the various cationically polymerizable organic compounds and radically polymerizable organic compounds specifically described above can be used.

[0043] The curable resin composition of the present invention may contain an active energy ray-sensitive cationic polymerization initiator (hereinafter may be simply referred to as a "cationic polymerization initiator") and / or an active energy ray-sensitive radical polymerization initiator (hereinafter may be simply referred to as a "radical polymerization initiator").

[0044] <<Cationic polymerization initiator>> As the cationic polymerization initiator, any polymerization initiator capable of initiating the cationic polymerization of a cationic polymerizable organic compound can be used. Among them, as the cationic polymerization initiator, an onium salt that releases a Lewis acid when irradiated with active energy rays is preferably used. Examples of such onium salts include aromatic sulfonium salts of Group VIIa elements, aromatic onium salts of Group VIa elements, and aromatic onium salts of Group Va elements. More specifically, for example, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis-[4-(diphenylsulfonio)phenyl]sulfide bisdihexafluoroantimonate, bis-[4-(di-4'-hydroxyethoxyphenylsulfonio)phenyl]sulfide bisdihexafluoroantimonate, bis-[4-(diphenylsulfonio)phenyl]sulfide bisdihexafluorophosphate, diphenyliodonium tetrafluoroborate, and those represented by the following chemical formula: [ka] (X = SbF6, PF6, (CF3-CF2)3PF3 or Ga(C6F5)4) [ka] Some examples include: The cationic polymerization initiator may be used alone or in combination of two or more kinds. Alternatively, one or more kinds of the above-mentioned cationic polymerization initiators may be used in combination with other cationic polymerization initiators.

[0045] For the purpose of improving the reaction rate, a photosensitizer such as benzophenone, benzoin alkyl ether, thioxanthone, or dialkoxyanthracene may be used together with the cationic polymerization initiator, if necessary.

[0046] <<Radical polymerization initiator>> As the radical polymerization initiator, any polymerization initiator capable of initiating radical polymerization of a radically polymerizable organic compound upon irradiation with active energy rays can be used, such as benzil or its dialkyl acetal compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, and thioxanthone compound.

[0047] Examples of benzyl or its dialkyl acetal compounds include benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, and 1-hydroxycyclohexyl phenyl ketone. 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, and p-azidobenzalacetophenone.

[0048] Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether. Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, and 4,4'-dichlorobenzophenone. Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

[0049] These radical polymerization initiators may be used alone or in combination of two or more kinds.

[0050] The curable resin composition of the present invention contains, based on the total mass of the curable resin composition, preferably 30 to 85 mass%, more preferably 40 to 80 mass%, and even more preferably 45 to 75 mass% of the cationic polymerizable organic compound (A), and preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and even more preferably 15 to 30 mass% of the radical polymerizable organic compound (B), from the viewpoints of the viscosity of the composition, reaction rate, modeling rate, toughness, impact resistance, durability, heat distortion temperature (heat resistance), dimensional accuracy, mechanical properties, etc. of the composition. As described above, the content of the one-end-capped polyalkylene oxide compound represented by the above formula (I) is preferably 1 to 30 mass%, more preferably 1 to 25 mass%, and even more preferably 5 to 25 mass% based on the total mass of the curable resin composition. In addition, when the curable resin composition of the present invention contains a cationic polymerization initiator and / or a radical polymerization initiator, the cationic polymerization initiator is contained in an amount of preferably 0.1 to 10 mass %, more preferably 0.5 to 8 mass %, and even more preferably 1 to 5 mass %, and the radical polymerization initiator is contained in an amount of preferably 0.1 to 10 mass %, more preferably 0.5 to 8 mass %, and even more preferably 1 to 4 mass %.

[0051] The curable resin composition of the present invention contains a cationic polymerizable organic compound (A), but as described above, the reaction rate of the cationic polymerizable organic compound is slow, and it takes time to model. Therefore, the curable resin composition of the present invention preferably contains an oxetane compound to promote cationic polymerization. When an oxetane compound, particularly an oxetane monoalcohol compound, is contained in the curable resin composition containing the cationic polymerizable organic compound (A), a white three-dimensional object having high whiteness and excellent sliding properties can be more smoothly manufactured.

[0052] <<Oxetane compounds>> As the oxetane compound, one or more of a monooxetane compound having one oxetane group in the molecule and a polyoxetane compound having two or more oxetane groups in one molecule can be used.

[0053] When the oxetane compounds are a monooxetane compound having one oxetane group per molecule and a polyoxetane compound having two or more oxetane groups per molecule, and a mass ratio (monoxetane compound:polyoxetane compound) of preferably 95:5 to 5:95, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20 is used, the water and moisture absorption rate of the resin composition for optically three-dimensional objects in high humidity conditions is reduced, the initial high curing sensitivity can be maintained for a long period of time, and the mechanical properties such as toughness of the three-dimensional objects obtained by photolithography are improved.

[0054] As the monooxetane compound, any compound having one oxetane group per molecule can be used, but in particular, a monooxetane monoalcohol compound having one oxetane group and one alcoholic hydroxyl group per molecule is preferably used. Among the above monooxetane monoalcohol compounds, at least one selected from the group consisting of monooxetane monoalcohol compounds represented by the following general formula (II-1a) and monooxetane monoalcohol compounds represented by the following general formula (II-2a) is more preferably used as the monooxetane compound, in terms of ease of availability, high reactivity, and low viscosity.

[0055] [ka] (In the formula, R 11 and R 12 is an alkyl group having 1 to 5 carbon atoms, R 13 represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.

[0056] In the above general formula (II-1a), R 11 Examples of the aryl group include methyl, ethyl, propyl, butyl, and pentyl. Specific examples of the monooxetane alcohol (II-1a) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-n-butyloxetane, 3-hydroxymethyl-3-propyloxetane, etc., and one or more of these can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferably used from the viewpoints of availability, reactivity, etc.

[0057] In the above general formula (II-2a), R 12 Examples of the aryl group include methyl, ethyl, propyl, butyl, and pentyl. In the above general formula (II-2a), R 13R may be either a linear or branched alkylene group as long as it is an alkylene group having 2 to 10 carbon atoms, or may be a linear or branched alkylene group having 2 to 10 carbon atoms and an ether bond (ether-type oxygen atom) in the middle of the alkylene group (alkylene chain). 13 Specific examples of R include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and a 3-oxypentylene group. Among these, R is particularly preferred from the viewpoints of ease of synthesis and ease of handling since the compound is a liquid at room temperature. 13 is preferably a trimethylene group, a tetramethylene group, a pentamethylene group or a heptamethylene group.

[0058] Specific examples of the oxetane monoalcohol compound include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-normal butyloxetane, 3-hydroxymethyl-3-phenyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxetane, 3-hydroxyethyl-3-propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane, 3-hydroxypropyl-3-phenyloxetane, 3-hydroxybutyl-3-methyloxetane, and 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane. One or more of these may be used. Among these, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, and 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane are preferably used from the viewpoint of availability, etc. For example, 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane has an alkylene group of an appropriate length, so that it is difficult to mix with water and is unlikely to cause problems such as moisture absorption in summer.

[0059] As the polyoxetane compound having two or more oxetane groups in one molecule, any of compounds having two oxetane groups, compounds having three or more oxetane groups, and compounds having four or more oxetane groups can be used, but dioxetane compounds having two oxetane groups are preferably used. Among them, dioxetane compounds represented by the following general formula (II-b) are preferred in terms of availability, reactivity, low moisture absorption, and mechanical properties of the cured product. [ka] (In the formula, R 12 represents an alkyl group having 1 to 5 carbon atoms, and R 14 may be the same or different, and each represents an alkyl group having 1 to 5 carbon atoms; R 15 represents a divalent organic group having or not having an aromatic ring, and s represents an integer of 0 or 1.

[0060] R in the above general formula (II-b) 12 As in the general formula (II-2a), examples of the aryl group include methyl, ethyl, propyl, butyl, and pentyl. R 14 Examples of the aryl group include methyl, ethyl, propyl, butyl, and pentyl. R 15 Examples of the alkylene group include a linear or branched alkylene group having 1 to 12 carbon atoms (such as an ethylene group, a propylene group, a butylene group, a neopentylene group, an n-pentamethylene group, an n-hexamethylene group, etc.), a divalent group represented by the formula: -CH2-Ph-CH2- or -CH2-Ph-Ph-CH2-, a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol AD ​​residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, a tricyclodecanedimethanol residue, a terephthalic acid residue, an isophthalic acid residue, and an o-phthalic acid residue.

[0061] Specific examples of the dioxetane compound (II-b) include the dioxetane compounds represented by the following formula (II-1b) or formula (II-2b). [ka] (In the formula, R 16 may be the same or different groups, and each represents an alkyl group having 1 to 5 carbon atoms; R 17 represents a divalent organic group that may or may not have an aromatic ring.

[0062] Specific examples of the dioxetane compound represented by the above formula (II-1b) include bis(3-methyl-3-oxetanylmethyl) ether, bis(3-ethyl-3-oxetanylmethyl) ether, bis(3-propyl-3-oxetanylmethyl) ether, and bis(3-butyl-3-oxetanylmethyl) ether. Specific examples of the dioxetane compound represented by the above formula (II-2b) include those in which the two R 16 are both methyl, ethyl, propyl, butyl, or pentyl groups, and R 17 can be an ethylene group, a propylene group, a butylene group, a neopentylene group, an n-pentamethylene group, an n-hexamethylene group, a divalent group represented by the formula -CH2-Ph-CH2- or -CH2-Ph-Ph-CH2-, a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol AD ​​residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, a tricyclodecanedimethanol residue, a terephthalic acid residue, an isophthalic acid residue, or an o-phthalic acid residue.

[0063] Among them, the polyoxetane compound (II-2b) is preferably a compound represented by the formula 16In terms of availability, low moisture absorption, and mechanical properties of the cured product, bis(3-methyl-3-oxetanylmethyl) ether and / or bis(3-ethyl-3-oxetanylmethyl) ether, in which both are methyl or ethyl groups, are preferably used, and in particular bis(3-ethyl-3-oxetanylmethyl) ether is more preferably used.

[0064] When the oxetane compound is contained in the curable resin composition of the present invention, it is more preferable to contain it in the range of preferably 5 to 40 mass %, more preferably 10 to 30 mass %, based on the mass of the cationically polymerizable organic compound (A). By setting the content of the oxetane compound in the above range, a domain formed by the polyalkylene oxide chain of the one-end-capped polyalkylene oxide compound grows in the matrix made of the cured resin, and a white shaped object having high whiteness and sliding property can be smoothly produced at a high modeling speed.

[0065] The curable resin composition of the present invention may contain, as necessary, one or more suitable amounts of colorants such as pigments and dyes, defoamers, leveling agents, thickeners, flame retardants, antioxidants, fillers (silica, glass powder, ceramic powder, metal powder, etc.), modifying resins, etc., as long as the effects of the present invention are not impaired.

[0066] <Method of manufacturing 3D objects> The white three-dimensional object of the present invention is produced by repeating the above-mentioned modeling operation of irradiating an active energy ray onto a modeling surface made of the curable resin composition to form one cured resin layer having a predetermined shape pattern, applying one layer of an active energy ray-curable resin composition onto the cured resin layer to form a modeling surface, and irradiating the modeling surface with an active energy ray to form one cured resin layer having a predetermined shape pattern. According to the present invention, there is provided a method for producing this white three-dimensional object, and a white three-dimensional object obtained by the method. Examples of active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequency waves. Among them, ultraviolet rays having a wavelength of 300 to 400 nm are preferably used from an economical viewpoint, and as the light source, an ultraviolet laser (e.g., Ar laser, He-Cd laser, solid-state laser, etc.), a mercury lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, etc. can be used. In particular, a laser light source is preferably used because it can increase the energy level to shorten the modeling time, and has excellent light collecting properties to obtain high modeling accuracy.

[0067] In the present invention, the term "white" refers to a plastic-like white color, and is characterized, for example, by haze value and total light transmittance. In the present invention, the haze of the three-dimensional object is preferably 15% or more, more preferably 75% or more, even more preferably 80% or more, and even more preferably 90% or more. In the present invention, the total light transmittance of the three-dimensional object is preferably less than 50%, more preferably 15% or less, and further preferably 10% or less. When the haze value and the total light transmittance are within the above ranges, respectively, a three-dimensional object can be obtained that exhibits a more plastic-like white color.

[0068] <White three-dimensional object> The white three-dimensional object of the present invention obtained by the above method has a plastic-like white appearance and is also excellent in mechanical properties such as sliding property, etc. There are no limitations on the overall shape, dimensions, uses, etc. of the white three-dimensional object of the present invention. Representative uses of the white shaped object of the present invention include models for verifying the appearance design during the design process, models for checking the functionality of parts, mother molds for producing casting molds, base models for producing metal molds, parts having a minute and complex structure, three-dimensional parts having a complex structure, and other practical products. In particular, the white shaped object of the present invention has a plastic-like appearance and is effective as a model of a precision part, a part having a minute and complex structure, a three-dimensional part having a complex structure, and other practical products. In addition, since it has excellent sliding properties, it is also effective as a sliding member. Specifically, it can be effectively used for models, mother molds, processing, and in some cases actual parts of precision parts, electric and electronic parts, furniture, architectural structures, automotive parts, various containers, and castings. EXAMPLES

[0069] In the following, examples are shown to more specifically explain the present invention, but the present invention is not limited to these examples. In the examples, "parts" means parts by mass.

[0070] [Measurement method] Various physical properties in the examples and comparative examples were measured by the following methods. (1) Total light transmittance of the object Using the objects [rectangular test pieces with a width of 20 mm, height of 45 mm, and thickness of 10 mm (measurement surface)] produced in the following Examples and Comparative Examples, the spectral transmittance was measured for the standard illuminant D65 and a 2-degree visual field using a Hitachi High-Technologies Corporation UV-3900H ultraviolet-visible spectrophotometer and an integrating sphere to determine the total light transmittance as defined in JIS K-7375.

[0071] (2) Haze value of the object Using the objects [rectangular test pieces with a width of 20 mm, height of 45 mm, and thickness of 10 mm (measurement surface)] produced in the following Examples and Comparative Examples, the spectral transmittance was measured for the standard illuminant D65 and a 2-degree visual field using a Hitachi High-Technologies Corporation UV-3900H ultraviolet-visible spectrophotometer and an integrating sphere to determine the haze defined in JIS K-7136.

[0072] (3) Sliding properties of the model Two objects [rectangular test pieces with a width of 20 mm, height of 45 mm, and thickness of 10 mm (measurement surface)] produced in the following Examples and Comparative Examples were used, with the 20 mm x 45 mm faces brought into contact with each other and slid in that state at a constant speed, and the resistance felt in the hand at that time was evaluated. A rating of 3 was given for something that moved at a constant sliding speed with almost no resistance and with a constant force; a rating of 2+ for something that caught a little but not as bad as the rating of 2 below; a rating of 2 for something that caught occasionally; a rating of 1+ for something that caught frequently and was difficult to slide at a constant speed; a rating of -1 for something that was extremely difficult to slide at a constant speed; and a rating of -2 for something that was barely able to slide at all. Using the objects produced in the following Examples and Comparative Examples [a rectangular test piece measuring 5 mm wide, 10 mm high, and 10 mm thick, and a square test piece measuring 50 mm wide, 50 mm high, and 2 mm thick], measurements were taken using a "TL201Tt" made by Trinity Lab Co., Ltd., with a load of 50 g, a measurement distance of 50 mm, a measurement speed of 1 mm / s, and the rectangular test piece being moved over the square test piece with a measurement surface of 5 mm x 10 mm.

[0073] (4) Impact strength of the model Notched test pieces conforming to JIS K-7110 were prepared from the objects produced in the following Examples and Comparative Examples using a Tester Sangyo notching machine, and the Izod impact strength of the notched test pieces conforming to JIS K-7110 was measured using a Toyo Seiki Co., Ltd. digital impact tester "Model DG-18."

[0074] The following were used as components constituting the resin compositions of the respective Examples and Comparative Examples. <Cationically polymerizable organic compound (A)> ··2021P: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (Celloxide 2021P) HBE-100: Hydrogenated bisphenol A diglycidyl ether (Rikaresin HBE-100, manufactured by New Japan Chemical Co., Ltd.) BPO-20E: Bisphenol A bis(propylene glycol glycidyl ether) ether (Rikaresin BPO-20E, manufactured by New Japan Chemical Co., Ltd.) ··EX-321: Trimethylolpropane polyglycidyl ether (Denacol EX-321, Nagase ChemteX Corporation) <Radical polymerizable organic compound (B)> ··A-9550W: Dipentaerythritol polyacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) ATM-4P: Prolene oxide modified pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) A-BPE-4: 2,2-bis[4-(acryloxydiethoxy)phenyl]propane (NK Ester A-BPE-4, manufactured by Shin-Nakamura Chemical Co., Ltd.) A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0075] <One-end-capped polyalkylene oxide compound represented by formula (I)> MB-90: Polyoxypropylene butyl ether (C4H9O[C3H6O] n H (n=90), Acrobute (registered trademark) MB-90, manufactured by NOF Corporation) MB-52: Polyoxypropylene butyl ether (C4H9O[C3H6O] n H (n=52), Acrobute (registered trademark) MB-52, manufactured by NOF Corporation) <Polyalkylene oxide compound> PTG-L3500: Polytetramethylene glycol (number average molecular weight 3500, manufactured by Hodogaya Chemical Co., Ltd.) PTG-2000SN: Polytetramethylene glycol (number average molecular weight 2000, manufactured by Hodogaya Chemical Co., Ltd.) PTG-850SN: Polytetramethylene glycol (number average molecular weight 850, manufactured by Hodogaya Chemical Co., Ltd.) A-PTMG-65: Polytetramethylene glycol #650 diacrylate (molecular weight 758, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0076] <Oxetane compounds> EHO: 3-ethyl-3-hydroxymethyloxetane (ETERNACOLL® EHO, Ube Industries) OXT-221: 3-Ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (Toagosei) HBOX: 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane (ETERNACOLL® HBOX, Ube Industries) <Cationic polymerization initiator> (All manufactured by San-Apro Co., Ltd.) [ka] CPI-101A: (X=SbF6) ·CPI-200K:(X=(CF3-CF2)3PF3) CPI-100B(40): [ka] <Radical polymerization initiator> A-184: 1-Hydroxycyclohexyl-phenyl ketone (Omnirad 184, IGM Resins)

[0077] Example 1 The components shown in Table 1 were thoroughly mixed to prepare a curable resin composition for white objects. The obtained curable resin composition for white objects was used in an ultra-high speed stereolithography system ("RM-3000" manufactured by Nabtesco Corporation) to perform a liquid surface irradiation energy of 80 mJ / cm using a semiconductor laser (rated output 200 mW; wavelength 355 nm; manufactured by Spectra Physics Corporation). 2 Under these conditions, optical 3D modeling was performed with a slice pitch (layer thickness) of 0.10 mm and an average modeling time of 2 minutes per layer to produce test pieces for measuring physical properties ([rectangular test pieces with a width of 5 mm, height of 10 mm, and thickness of 10 mm, and square test pieces with a width of 50 mm, height of 50 mm, and thickness of 2 mm]) and 10 mm thick test pieces for measuring haze and total light transmittance. The obtained test pieces were irradiated with ultraviolet light (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm 2 ) was irradiated for 10 minutes and post-cured. The haze, total light transmittance and impact strength of the post-cured test pieces were measured by the methods described above, and the results are shown in Table 1 below.

[0078] Examples 1a, 2, 2a, 3-4, Comparative Examples 1-1 to 1-3, 2-1 to 2-2, 3-3 Curable resin compositions for white objects were prepared in the same manner as in Example 1, except that the compositions were changed to those shown in Tables 1 and 2. Test pieces were prepared and the haze, total light transmittance, and impact strength of the test pieces after curing were measured. The results are shown in Tables 1 and 2.

[0079] [Table 1] [Table 2] [Table 3]

[0080] Comparing the Examples and Comparative Examples, it is clear that the three-dimensional objects produced using the curable resin composition of the present invention have the properties of photo-induced moldings, such as impact strength, but also have a plastic-like white appearance and are excellent in mechanical properties, such as sliding properties.

Claims

1. A curable resin composition for white three-dimensional objects, comprising a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), and a one-end-capped polyalkylene oxide compound represented by formula (I). 【Chemistry 1】 [In the formula, R １ and R ２ may be the same or different, and each independently represents at least one alkylene group having 2 to 8 carbon atoms, m represents an integer of 20 to 200, n represents an integer of 0 to 100, and X represents at least one alkyl group having 1 to 8 carbon atoms.

2. 2. The curable resin composition for a white three-dimensional object according to claim 1, wherein the one-end-capped polyalkylene oxide compound represented by formula (I) has a number average molecular weight of 500 to 20,000.

3. The curable resin composition for a white three-dimensional object according to claim 1 or 2, wherein the cationically polymerizable organic compound (A) is a compound having an epoxy group.

4. The curable resin composition for a white three-dimensional object according to claim 1 or 2, wherein the radical polymerizable organic compound (B) is a compound having a (meth)acrylic group.

5. The curable resin composition for a white three-dimensional object according to claim 1 or 2, further comprising an oxetane compound.

6. 3. The curable resin composition for a white three-dimensional object according to claim 1, comprising 1 to 30% by mass of the one-end-capped polyalkylene oxide compound represented by formula (I).

7. A method for producing a white three-dimensional object, comprising irradiating the curable resin composition for a white three-dimensional object according to claim 1 or 2 with active energy rays.

8. A white three-dimensional object obtained by curing the curable resin composition for a white three-dimensional object according to claim 1 or 2.

Images