Composition for three-dimensional molding

Abstract

To provide a resin composition for three-dimensional molding that has low viscosity yet can yield three-dimensional molded articles with high strength and heat resistance.SOLUTION: A composition for three-dimensional molding comprises radical-polymerizable compounds comprising 1-40 mass% of a monofunctional radical-polymerizable compound with a saturated ring structure and 60-99 mass% of a polyfunctional radical-polymerizable compound with a saturated ring structure. Relative to 100 pts.mass of the radical-polymerizable compounds, the composition also contains 0.1-10 pts.mass of a radical photoinitiator and 60-400 pts.mass of an inorganic filler.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition for three-dimensional modeling and a three-dimensional model obtained by photocuring the composition. [Background technology]

[0002] There are two types of three-dimensional photo-fabrication methods: SLA (stereolithography) and DLP (digital light processing). There are applications where heat resistance is required, such as for molds. If a multifunctional monomer is used to improve the heat resistance of a three-dimensional object, the strength is insufficient. In addition, if a metal oxide is added to impart heat resistance, the strength is insufficient and the viscosity of the composition increases, resulting in defective modeling.

[0003] Patent Document 1 discloses a three-dimensional object using acryloylmorpholine and tricyclodecane dimethanol diacrylate in combination. However, there is no mention of inorganic fillers. With such a composition, it is difficult to achieve both heat resistance and strength. In addition, when an inorganic filler is blended, the workability associated with the increase in viscosity of the composition and the dispersion stability of the inorganic filler also become problems. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2022-70123 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin composition for three-dimensional modeling, which has a low viscosity but is capable of producing a three-dimensional model having high strength and heat resistance. [Means for solving the problem]

[0006] After extensive investigation, the inventors discovered that by containing a specific radically polymerizable compound and a specific amount of an inorganic filler, it is possible to obtain a three-dimensional object having high strength and heat resistance while having low viscosity, and thus completed the present invention.

[0007] That is, the present invention (1) contains a radical polymerizable compound containing 1 to 40 mass % of a monofunctional radical polymerizable compound having a saturated ring structure and 60 to 99 mass % of a polyfunctional radical polymerizable compound having a saturated ring structure, The composition for three-dimensional modeling further contains 0.1 to 10 parts by mass of a radical photoinitiator and 60 to 400 parts by mass of an inorganic filler relative to 100 parts by mass of the radical polymerizable compound.

[0008] The present invention (2) is the composition for three-dimensional modeling according to the present invention (1), wherein at least one of the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound has a nitrogen-containing heterocycle.

[0009] The present invention (3) is also directed to the monofunctional radical polymerizable compound comprising (meth)acryloylmorpholine, the polyfunctional radical polymerizable compound contains tricyclodecane dimethanol di(meth)acrylate, The inorganic filler contains silica having an average particle size of 0.1 to 8 μm. The present invention relates to a composition for three-dimensional modeling, the composition being described in (1) or (2).

[0010] The present invention (4) is the composition for three-dimensional forming according to any one of the present inventions (1) to (3), wherein the inorganic filler has a (meth)acrylic group on the surface.

[0011] The present invention (5) is the composition for three-dimensional modeling according to any one of the present inventions (1) to (4), which has a viscosity at 30° C. of 100 to 3000 mPa·s.

[0012] The present invention (6) is the composition for three-dimensional modeling according to any one of the present inventions (1) to (5), which is used in an SLA apparatus using a top irradiation wavelength of 405 nm or less.

[0013] The present invention (7) is the composition for three-dimensional modeling according to any one of the present inventions (1) to (5), which is used in a DLP device using a top irradiation wavelength of 455 nm or less.

[0014] The present invention (8) is the composition for three-dimensional modeling according to any one of the present inventions (1) to (7), which is used for producing a resin mold.

[0015] The present invention (9) provides a three-dimensional object obtained by curing the composition for three-dimensional object formation according to any one of the present inventions (1) to (8), This three-dimensional object has a deflection temperature under load of 180°C or higher and a bending strength of 150 MPa or higher, as measured by the edgewise method at a load of 0.45 MPa in accordance with ASTM D648.

[0016] The present invention (10) is a three-dimensional object obtained by curing the composition for three-dimensional object formation according to any one of the present inventions (1) to (8), This three-dimensional object has a deflection temperature under load of 120°C or higher and a bending strength of 150 MPa or higher, as measured by the edgewise method at a load of 1.8 MPa in accordance with ASTM D648.

[0017] The present invention (11) relates to the three-dimensional structure according to the present invention (9) or (10), wherein the weight loss rate at 300° C. as measured by TG-DTA is 0.5% or less.

[0018] Further, the present invention (12) provides a method for producing a three-dimensional object by using the composition for three-dimensional object formation according to any one of the present inventions (1) to (8), A process of surface treating the obtained three-dimensional object with a fluorine silane coating liquid. The present invention relates to a method for producing a three-dimensional object, comprising the steps of:

[0019] The present invention (13) is the method for producing a three-dimensional object according to the present invention (12), wherein the three-dimensional object is a resin mold. Effect of the Invention

[0020] The resin composition for three-dimensional modeling of the present invention has low viscosity, yet can produce three-dimensional objects having high strength and heat resistance, and can be suitably used in SLA or DLP three-dimensional photolithography devices. [Brief description of the drawings]

[0021] [Figure 1] FIG. 2 is a schematic diagram for explaining a process of forming a three-dimensional object by stereolithography using a resin composition for three-dimensional modeling according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] <<Composition for three-dimensional modeling>> The composition for three-dimensional modeling of the present invention contains radical polymerizable compounds including 1-40% by mass of a monofunctional radical polymerizable compound having a saturated ring structure and 60-99% by mass of a polyfunctional radical polymerizable compound having a saturated ring structure, and further contains 0.1-10 parts by mass of a radical photoinitiator and 60-400 parts by mass of an inorganic filler relative to 100 parts by mass of the radical polymerizable compound. Since strength is highly dependent on the breaking elongation, the present invention is based on the concept of improving strength by increasing the breaking elongation by reducing the crosslink density, and compensating for the elastic modulus and heat resistance reduced by the reduction in crosslink density with an inorganic filler.

[0023] Regarding the monofunctional radical polymerizable compound having a saturated ring structure, examples of the saturated ring structure include a morpholyl structure, an isobornyl structure, a cyclodecane structure, a dicyclodecane structure, a tricyclodecane structure, a dicyclopentane structure, a cyclohexane structure, an adamantane structure, an isocyanuric structure, etc. Examples of the monofunctional radical polymerizable compound having a saturated ring structure include (meth)acryloylmorpholine, (meth)acrylic acid isobornyl, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, etc.

[0024] The content of the monofunctional radically polymerizable compound having a saturated ring structure in the radically polymerizable compound is 1 to 40% by mass, preferably 10 to 30% by mass. If it is less than 1% by mass, the strength tends to be insufficient, and if it exceeds 40% by mass, the heat resistance tends to be insufficient.

[0025] Regarding the polyfunctional radical polymerizable compound having a saturated ring structure, the polyfunctional group may be two or more, and although there is no upper limit, it is preferable that the functional group is four or less. Examples of the saturated ring structure include a morpholyl structure, an isobornyl structure, a cyclodecane structure, a dicyclodecane structure, a tricyclodecane structure, a dicyclopentane structure, a cyclohexane structure, an adamantane structure, and an isocyanuric structure. Examples of the polyfunctional radical polymerizable compound having a saturated ring structure include a tricyclodecane dimethanol di(meth)acrylate.

[0026] The content of the polyfunctional radically polymerizable compound having a saturated ring structure in the radically polymerizable compound is 60 to 90% by mass, preferably 60 to 80% by mass. If it is less than 60% by mass, the heat resistance tends to be insufficient, and if it exceeds 90% by mass, the strength tends to be insufficient.

[0027] At least one of the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound preferably has a nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle structure include a morpholyl structure and an isocyanuric structure. For example, an example of the monofunctional radical polymerizable compound is (meth)acryloylmorpholine, and examples of the polyfunctional radical polymerizable compound are tris 2-hydroxyethyl isocyanurate tri(meth)acrylate and tris 2-hydroxyethyl isocyanurate di(meth)acrylate.

[0028] The radical polymerizable compound may contain a radical polymerizable compound other than the monofunctional radical polymerizable compound having a saturated ring structure and the polyfunctional radical polymerizable compound having a saturated ring structure.

[0029] Examples of monofunctional radical polymerizable compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, neopentyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cetyl (meth)acrylate, ethyl carbitol (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, polyalkylene glycol ether (meth)acrylate, polyalkylene glycol (meth)acrylate, etc. Examples of (meth)acrylic acid esters include acrylates, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, Nt-butyl(meth)acrylamide, N-octyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and diacetone(meth)acrylamide and other (meth)acrylic acid amides, styrene, methyl itaconate, ethyl itaconate, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, N-vinylcaprolactam, 3-vinyl-5-methyl-2-oxazolidinone, and polyalkylene glycol mono(meth)acrylates.

[0030] Examples of the polyfunctional radically polymerizable compound include (meth)acrylic acid esters such as ditrimethylolpropane tetraacrylate, and polyalkylene glycol di(meth)acrylates.

[0031] The content of radical polymerizable compounds other than monofunctional radical polymerizable compounds having a saturated ring structure and polyfunctional radical polymerizable compounds having a saturated ring structure is preferably 0 to 20 mass %, more preferably 0 to 10 mass %.

[0032] The radical polymerizable compound is preferably a compound whose homopolymer has a glass transition temperature of 80° C. or higher, preferably 100° C. or higher. If the temperature is lower than 80° C., the heat resistance tends to be poor. Here, the glass transition temperature may be measured by actually polymerizing the homopolymer, or may be calculated by the atomic group contribution method.

[0033] <Radical photoinitiator> The radical photoinitiator is activated by the action of light to generate radicals and initiate polymerization of the radical polymerizable compound. Examples of the radical photopolymerization initiator include an alkylphenone-based photopolymerization initiator and an acylphosphine oxide-based photopolymerization initiator.

[0034] Examples of alkylphenone-based photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and the like.

[0035] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

[0036] The content of the radical photoinitiator is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the radical polymerizable compound. If it is less than 0.1 part by mass, curing tends to be insufficient, and if it exceeds 10 parts by mass, storage stability tends to be poor and curing tends to be insufficient due to absorption.

[0037] <Inorganic filler> The inorganic filler is not particularly limited, but examples thereof include inorganic fillers and organic fillers having a crosslinked structure. Specific examples of the material of the inorganic filler include, for example, colloidal silica, hollow silica, fumed silica, and other silica, and metal oxides such as titania and zirconia, as well as core-shell type acrylic-silica composites in which thermoplastic or thermosetting acrylic resin is coated with silica, core-shell type melamine-silica composites in which melamine resin is coated with silica, core-shell type acrylic-silica composites in which silica is coated with thermoplastic or thermosetting acrylic resin, core-shell type melamine-silica composites in which silica is coated with melamine resin, and organic-inorganic composites such as acrylic-silica composites in which small silica is supported by thermoplastic or thermosetting acrylic resin. Specific examples of the material of the organic filler are not particularly limited, but examples thereof include fluororesins, acrylic resins, melamine resins, and urethane rubber.

[0038] The average particle size of the inorganic filler is not particularly limited, but is preferably 0.1 to 8 μm, more preferably 0.3 to 5 μm, and even more preferably 0.5 to 1.5 μm. If it is less than 0.1 μm, the viscosity tends to be high, and if it exceeds 8 μm, the sedimentation stability tends to be poor.

[0039] It is preferable that the inorganic filler has a (meth)acrylic group on the surface. Such a functional group can be introduced to the surface of the inorganic filler by treating the inorganic filler with a silane coupling agent having a (meth)acrylic group.

[0040] The content of the inorganic filler is 60 to 400 parts by mass, and preferably 100 to 300 parts by mass, relative to 100 parts by mass of the radical polymerizable compound. If it is less than 60 parts by mass, the heat resistance tends to be insufficient, and if it exceeds 400 parts by mass, the viscosity tends to be high.

[0041] <Additives> The resin composition for three-dimensional modeling of the present invention may contain known additives such as polymerization inhibitors, chain transfer agents, wax particles, dyes, UV sensitizers, plasticizers, UV absorbers, pigments, surfactants, and light absorbers.

[0042] Examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, methylhydroquinone, tert-butyl-hydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine, 2,6-diisobutylphenol, 2,6-di-tert-butyl-4-methylphenol, ammonium-N-nitrosophenylhydroxylamine, ammonium N-nitrosophenylhydroxylamine, etc. The amount of the polymerization inhibitor is preferably 0.001 to 1.0% by mass, more preferably 0.01 to 0.3% by mass, in the entire resin composition.

[0043] By blending a chain transfer agent, the polymerization degree of the reactive monomer (the molecular weight of the polymer composed of the reactive monomer) can be controlled. Examples of the chain transfer agent include polyol, water, thiol group-containing compounds such as 3-mercaptopropylmethyldimethoxysilane, 1,4-bis(3-mercaptobutyryloxy)butane, and pentaerythritol tetrakis(3-mercaptobutyrate). The blending amount of the chain transfer agent is preferably 0.00001 to 10 mass% of the total resin composition, and more preferably 0.0001 to 1 mass%. Examples of the polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0044] By blending a light absorbent, it is possible to more easily control the curing property. Examples of light absorbents include 2,5-bis(5-tert-butyl-2-benzoxazolylthiophene). The blending amount of the light absorbent is preferably 0.001 to 0.5 mass % and more preferably 0.005 to 0.1 mass % in the total resin composition.

[0045] The resin composition for three-dimensional modeling of the present invention is preferably liquid at room temperature. Being liquid at room temperature allows easy photo-modeling using a 3D printer or the like. The viscosity of the resin composition for three-dimensional modeling of the present invention at 30°C is preferably 100 to 3000 mPa·s, more preferably 200 to 1000 mPa·s. The viscosity of the resin composition can be measured at a rotation speed of 20 rpm using a cone-plate type E-type viscometer.

[0046] The resin composition for three-dimensional modeling of the present invention can form two-dimensional or three-dimensional objects (or patterns) by various modeling methods, and is particularly suitable for photo-modeling. The resin composition for three-dimensional modeling is liquid at room temperature, so it can be used, for example, in vat-type photo-modeling or ink-jet-type photo-modeling. It can be particularly suitably applied to a stereolithography (SLA) device using a top irradiation wavelength of 405 nm or less.

[0047] <<Three-dimensional objects>> The three-dimensional object of the present invention is a three-dimensional object obtained by curing the composition for three-dimensional object formation, and is characterized in that the deflection temperature under load measured by the edgewise method at a load of 0.45 MPa in accordance with ASTM D648 is 180°C or more and the flexural strength is 150 MPa or more, or the deflection temperature under load measured by the edgewise method at a load of 1.8 MPa in accordance with ASTM D648 is 120°C or more and the flexural strength is 150 MPa or more.

[0048] The deflection temperature under load, measured by the edgewise method at a load of 0.45 MPa in accordance with ASTM D648, is 180° C. or higher, preferably 250° C. or higher. The deflection temperature under load, measured by the edgewise method at a load of 1.8 MPa in accordance with ASTM D648, is 120° C. or higher, preferably 150° C. or higher.

[0049] The flexural strength is 150 MPa or more, preferably 170 MPa or more. If it is less than 150 MPa, the strength is insufficient. The flexural strength is measured in accordance with ASTM D790.

[0050] The Shore D hardness of the three-dimensional object of the present invention is not particularly limited, but is preferably D80 or more, and more preferably D85 or more. If it is less than D80, the strength tends to be insufficient. Here, the Shore D hardness is measured using a type D durometer in accordance with JIS K7215:1986.

[0051] The weight loss rate of the three-dimensional structure of the present invention at 300° C. as measured by TG-DTA is not particularly limited, but is preferably 0.5% or less, and more preferably 0.3% or less. If it exceeds 0.5%, it tends to be easily thermally decomposed.

[0052] The three-dimensional object of the present invention can be optimally applied to an SLA apparatus, in particular, an SLA using a top irradiation wavelength of 405 nm or less, or a DLP using a top irradiation wavelength of 455 nm or less.

[0053] The three-dimensional object of the present invention can be used for various purposes, including as a dental aligner molding mold, a resin mold, and an alternative to plastic injection moldings.

[0054] The three-dimensional object of the present invention can be produced by the method described below using the composition for three-dimensional modeling of the present invention. (1) forming a first liquid film made of the composition for three-dimensional object formation of the present invention, and curing the first liquid film to form a first pattern; and (2) A step of forming a second liquid film made of the resin composition for three-dimensional modeling of the present invention so as to be in contact with the first pattern, and curing the second liquid film to laminate the second pattern, thereby forming a three-dimensional object. Includes.

[0055] The procedure of the batt-type stereolithography will be described below with reference to Fig. 1. Fig. 1 shows an example of forming a three-dimensional object using a stereolithography device (patterning device) equipped with a resin tank (batt). In the illustrated example, a suspension-type modeling is shown, but there is no particular limitation as long as it is a method capable of three-dimensional modeling using a resin composition for three-dimensional modeling. There is also no particular limitation on the method of light irradiation (exposure), and it may be point exposure or surface exposure.

[0056] The optical molding apparatus 1 includes a platform 2 having a pattern formation surface 2a, a resin tank 3 containing a resin composition 5 for three-dimensional molding, and a projector 4 as a light source for a surface exposure method.

[0057] (1) A step of forming a first liquid film and curing it to form a first pattern. In step (1), as shown in (a), first, the pattern-forming surface 2a of the platform 2 is immersed in the resin composition for three-dimensional modeling 5 contained in the resin tank 3 while facing the projector 4 (the bottom surface of the resin tank 3). At this time, the height of the pattern-forming surface 2a (or the platform 2) is adjusted so that a liquid film 7a (liquid film a) is formed between the pattern-forming surface 2a and the projector 4 (or the bottom surface of the resin tank 3). Next, as shown in (b), the liquid film 7a is photocured by irradiating light L from the projector 4 toward it (surface exposure), thereby forming a first pattern 8a (pattern a).

[0058] In the optical molding apparatus 1, the resin tank 3 serves as a supply unit for the resin composition 5 for three-dimensional modeling. At least a portion of the resin tank 3 between the liquid film and the projector 4 (the bottom surface in FIG. 1) is desirably transparent to the exposure wavelength so that the liquid film is irradiated with light from a light source. The shape, material, size, etc. of the platform 2 are not particularly limited.

[0059] After the liquid film a is formed, the liquid film a is photocured by irradiating it with light from a light source. The light irradiation can be performed by a known method. The exposure method is not particularly limited, and may be point exposure or surface exposure. As the light source, a known light source used for photocuring can be used. In the case of the point exposure method, for example, a plotter method, a galvano laser (or galvano scanner) method, an SLA (stereolithography) method, etc. can be mentioned. The exposure wavelength can be appropriately selected depending on the constituents of the resin composition for three-dimensional modeling (particularly, the type of photopolymerization initiator).

[0060] (2) A process of forming a second liquid film in contact with the first pattern, and laminating the second pattern by curing the second liquid film to produce a three-dimensional object. In step (2), a three-dimensional modeling resin composition 5 is supplied between the pattern a obtained in step (1) and a light source to form a liquid film (liquid film b). That is, the liquid film b is formed on the pattern a formed on the pattern formation surface. The supply of the three-dimensional modeling resin composition 5 is the same as in step (1).

[0061] 1(c), after the first pattern 8a (two-dimensional pattern a) is formed, the first pattern forming surface 2a may be raised together with the platform 2. Then, by supplying a resin composition for three-dimensional printing 5 between the first pattern 8a and the bottom surface of the resin tank 3, a liquid film 7b (liquid film b) can be formed.

[0062] The formed liquid film b is exposed to light from a light source to photo-cure the liquid film b, and another pattern (pattern b obtained by photo-curing the liquid film b) is laminated on the first pattern a. By laminating the patterns in the thickness direction in this manner, a three-dimensional modeling pattern can be formed.

[0063] For example, as shown in (d) of FIG. 1, the liquid film 7b (liquid film b) formed between the first pattern 8a (pattern a) and the bottom surface of the resin tank 3 is exposed to light from the projector 4 to photo-cure the liquid film 7b. This photo-cure converts the liquid film 7b into the second pattern 8b (pattern b). In this way, the second pattern 8b can be laminated on the first pattern 8a. For the light source, exposure wavelength, etc., see the description of step (1).

[0064] Step (2) can be repeated multiple times. By repeating the process, multiple patterns b are stacked in the thickness direction, resulting in a more three-dimensional pattern. The number of repetitions can be appropriately determined depending on the shape and size of the desired three-dimensional object (three-dimensional pattern).

[0065] For example, as shown in (e) of FIG. 1, the platform 2 is raised in a state in which a first pattern 8a (pattern a) and a second pattern 8b (pattern b) are laminated on the pattern forming surface 2a. At this time, a liquid film 7b (liquid film b) is formed between the second pattern 8b and the bottom surface of the resin tank 3. Then, as shown in (f) of FIG. 1, the liquid film 7b is exposed to light from the projector 4, and the liquid film 7b is photocured. As a result, another pattern 8b (pattern b) is formed on the first pattern 8b. Then, by alternately repeating (e) and (f), a plurality of patterns 8b (two-dimensional patterns b) can be laminated.

[0066] It is preferable that the step (2) further includes a step of washing the first pattern and the second pattern with a solvent. Since the uncured resin composition for three-dimensional modeling adheres to the obtained three-dimensional modeling pattern, the step (2) is performed to remove the composition. Specific examples of the solvent include 3-methoxy-3-methyl-1-butanol.

[0067] The obtained three-dimensional modeling pattern may be post-cured as necessary. The post-curing may be performed by irradiating the pattern with light. The light irradiation conditions may be appropriately adjusted depending on the type of the resin composition for three-dimensional modeling and the degree of curing of the obtained pattern. The post-curing may be performed on a part of the pattern or on the entire pattern.

[0068] The method for producing a three-dimensional object of the present invention further comprises the steps of: A step of producing a three-dimensional object using the composition for three-dimensional modeling of the present invention; and A process of surface treating the obtained three-dimensional object with a fluorine silane coating liquid. The present invention is characterized by comprising:

[0069] The process of producing a three-dimensional object using the three-dimensional modeling composition of the present invention is as described above. By subjecting the three-dimensional object to a surface treatment with a fluorine silane coating liquid, the three-dimensional object can be given a mold-releasing function. Examples of the fluorine-based coating liquid include fluorine silicone-based materials. The method of surface treatment is not particularly limited, and examples include heat treatment. Since the mold-releasing property is improved by surface treatment with a fluorine-based coating liquid, it can be suitably applied to a resin mold. EXAMPLES

[0070] The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0071] Various chemicals used in the examples and comparative examples will be collectively described below.

[0072] <<Monofunctional radical polymerizable compound>> Acryloylmorpholine (ACMO, manufactured by KJ Chemicals Co., Ltd.)

[0073] <<Polyfunctional radical polymerizable compounds>> Tricyclodecane dimethanol diacrylate (IRR 214-K, Daicel Allnex Corporation) A mixture of 65% by mass of tris 2-hydroxyethyl isocyanurate triacrylate (first compound) and 35% by mass of tris 2-hydroxyethyl isocyanurate diacrylate (second compound) (M-313, manufactured by Toagosei Co., Ltd.)

[0074] <<Radical initiator>> 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (Omnirad TPO-H, IGM resin)

[0075] <<Light absorber>> 2,5-Bis(5-tert-butyl-2-benzoxazolylthiophene) (Nikkafluor OB, manufactured by Nippon Chemical Industry Co., Ltd.)

[0076] <<Polymerization inhibitor>> Methylhydroquinone (MeHQ, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0077] <<Inorganic filler>> Silica (SC2500-SMJ, manufactured by Admatechs Co., Ltd.), average particle size: 500 nm, treated with methacrylsilane

[0078] Examples 1 to 5 and Comparative Examples 1 to 2 The components were mixed in the amounts (mass ratios) shown in Table 1. The mixture was heated in an oven at 80°C while stirring to dissolve the solid components, thereby preparing a homogeneous liquid resin composition. The resulting resin composition was used to carry out the following evaluations. The evaluation results are shown in Table 1.

[0079] <Viscosity> The viscosity of the photocurable resin composition was measured at 30° C. and a rotation speed of 20 rpm using a cone-plate type E-type viscometer (TVE-20H, Toki Sangyo Co., Ltd.).

[0080] <Shore D hardness> Using an LCD-type 3D printer (Phrozen Shuffle XL, manufactured by Phrozen), rectangular samples (35 mm long x 20 mm wide x 6 mm thick (height)) were produced under conditions of 5 seconds of irradiation time per layer and 50 μm pitch in the z-axis (height direction). Shore D hardness was measured using a Type D durometer in accordance with JIS K7215:1986.

[0081] <Deflection temperature under load> Test pieces were prepared with a pitch of 50μm using an LCD 3D printer (Phrozen Shuffle XL, manufactured by Phrozen Corporation). Using these test pieces, the load deflection temperature (℃) was measured by the edgewise method at a load of 1.8MPa in accordance with ASTM D648, and the load deflection temperature (℃) was measured by the edgewise method at a load of 0.45MPa in accordance with ASTM D648.

[0082] <Bending strength> Test pieces were prepared at a pitch of 50 μm using an LCD 3D printer (Phrozen Shuffle XL, manufactured by Phrozen Corporation). The bending strength (MPa) of these test pieces was measured in accordance with ASTM D638.

[0083] <Weight loss rate at 300℃> Approximately 1 g of the resin composition prepared in each of the examples and comparative examples was sandwiched between glass plates and irradiated with 7 mW / cm using a UV irradiation device (manufactured by ITEC Systems Co., Ltd.). 2 The sample was heated from 50 to 900°C at a heating rate of 5°C / min using a DTG-60 (Shimadzu Corporation). The weight loss rate was calculated for the initial weight and the weight at 300°C.

[0084] [Table 1]

[0085] As shown in Table 1, Comparative Example 1 had high heat resistance and low viscosity, but low strength and weight loss rate, and Comparative Example 2, which contained silica compared to Comparative Example 1, had an improved weight loss rate, but had high viscosity and no improvement in strength was confirmed. On the other hand, Examples 1 to 5 contained a monocyclic acrylate, which is a saturated ring structure, and filled with silica, which led to improvements in viscosity and strength, and also had excellent heat resistance.

[0086] Examples 6 to 9 Test pieces were made with an LCD 3D printer (Phrozen Shuffle XL, manufactured by Phrozen) at a pitch of 50μm. The surfaces of these test pieces were then treated with the following three types of fluorosilane coating liquid. The contact angle of water was measured and found to be 76.4° without surface treatment, but 102.1°, 105.4°, and 97.2° after surface treatment with the following coating agents, respectively. All surface treatments produced water repellency, but treatment with FG-5084F130 produced the highest water repellency. Fluorine-based resin (NL-1, manufactured by Fluoro Technology Co., Ltd.) Fluorine resin (FG-5084F130, manufactured by Fluoro Technology Co., Ltd.) Fluorine resin (FG-5084F135, manufactured by Fluoro Technology Co., Ltd.) [Explanation of symbols]

[0087] 1:Stereolithography device 2: Platform 2a: Patterned surface 3:Resin tank 4: Projector 5: Composition for three-dimensional modeling 6: Release agent layer 7a: Liquid film a 7b: Liquid film b 8a: First pattern a 8b: Second pattern b L:Light

Claims

1. The composition contains a radical polymerizable compound containing 1 to 40% by mass of a monofunctional radical polymerizable compound having a saturated ring structure and 60 to 99% by mass of a polyfunctional radical polymerizable compound having a saturated ring structure, The composition for three-dimensional modeling further comprises, relative to 100 parts by mass of the radical polymerizable compound, 0.1 to 10 parts by mass of a radical photoinitiator and 60 to 400 parts by mass of an inorganic filler.

2. The composition for three-dimensional formation according to claim 1 , wherein at least one of the monofunctional radical polymerizable compound and the polyfunctional radical polymerizable compound has a nitrogen-containing heterocycle.

3. the monofunctional radically polymerizable compound contains (meth)acryloylmorpholine, the polyfunctional radical polymerizable compound contains tricyclodecane dimethanol di(meth)acrylate, The inorganic filler contains silica having an average particle size of 0.1 to 8 μm. The composition for three-dimensional modeling according to claim 1 or 2.

4. The composition for three-dimensional modeling according to claim 1 or 2, wherein the inorganic filler has a (meth)acrylic group on a surface thereof.

5. 3. The composition for three-dimensional modeling according to claim 1, having a viscosity at 30° C. of 100 to 3,000 mPa·s.

6. The composition for three-dimensional modeling according to claim 1 or 2, which is used in an SLA apparatus using a top irradiation wavelength of 405 nm or less.

7. The composition for three-dimensional modeling according to claim 1 or 2, which is used in a DLP device using a top irradiation wavelength of 455 nm or less.

8. The composition for three-dimensional modeling according to claim 1 or 2, which is used for producing a resin mold.

9. A three-dimensional object obtained by curing the composition for three-dimensional modeling according to claim 1 or 2, A three-dimensional object having a deflection temperature under load of 180°C or higher and a bending strength of 150 MPa or higher, as measured by the edgewise method at a load of 0.45 MPa in accordance with ASTM D648.

10. A three-dimensional object obtained by curing the composition for three-dimensional modeling according to claim 1 or 2, A three-dimensional object having a deflection temperature under load of 120°C or higher and a bending strength of 150 MPa or higher, as measured by the edgewise method at a load of 1.8 MPa in accordance with ASTM D648.

11. The three-dimensional structure according to claim 9, wherein the weight loss rate at 300° C. as measured by TG-DTA is 0.5% or less.

12. A step of producing a three-dimensional object using the composition for three-dimensional modeling according to claim 1 or 2; and A process of surface treating the obtained three-dimensional object with a fluorine silane coating liquid. A method for producing a three-dimensional object comprising the steps of:

13. The method for producing a three-dimensional object according to claim 12, wherein the three-dimensional object is a resin mold.

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