Wire rod for three-dimensional modeling, method for manufacturing three-dimensional modeling object, and three-dimensional modeling object

Abstract

Provided is a wire rod for three-dimensional molding, which is capable of three-dimensional molding by a hot melt deposition method. Provided are a three-dimensional molded article using a wire for three-dimensional molding, and a method for producing the three-dimensional molded article. The wire rod for three-dimensional molding contains a polyacetal resin, and has a difference (Tm2-Tc) between a melting point Tm2 and a crystallization temperature Tc measured by a differential scanning calorimeter of 22 DEG C to 40 DEG C, inclusive, and a melt flow rate of 0.8 g / 10 minutes to 8.0 g / 10 minutes, inclusive, measured at a temperature of 190 DEG C and a load of 2.16 kg.

Description

Technical Field

[0001] The present invention relates to a wire material for three-dimensional modeling, a method for manufacturing a three-dimensional modeling object, and a three-dimensional modeling object. Background Art

[0002] Since 3D printers can produce three-dimensional objects without the need for molds or large melting devices, they have rapidly become popular in recent years. As a modeling method using a 3D printer, known methods include hot melt deposition (FFF (Fused Filament Fabrication) method), stereolithography (STL (Stereolithography) method) and selective laser sintering (SLS (Selective Laser Sintering) method). Hot melt deposition is a method of forming a three-dimensional object by heating and melting a thermoplastic resin and then depositing it (for example, Patent Documents 1 and 2). Due to the low cost of the device, it is becoming more and more popular not only in industrial use but also in personal use.

[0003] Polyacetal resin is useful if it can be used as a modeling material for 3D printers because of its excellent mechanical properties.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2021-172084

[0007] Patent Document 2: Japanese Patent Application Publication No. 2019-131762 Summary of the invention

[0008] Since polyacetal resin shrinks more as the temperature decreases, it may warp when it is molded by the hot melt deposition method. In particular, when the size of the object is large, the surface in contact with the molding table may warp and peel off from the molding table during the molding process. In this case, three-dimensional molding using the hot melt deposition method becomes difficult.

[0009] The first object of the present disclosure is to provide a three-dimensional modeling wire that can be three-dimensionally modeled by a thermal melt deposition method. The second object of the present disclosure is to provide a three-dimensional modeled object using the three-dimensional modeling wire and a method for manufacturing the same.

[0010] The present disclosure has the following aspects.

[0011] [1] A wire material for three-dimensional modeling, comprising a polyacetal resin, and

[0012] The difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc measured by a differential scanning calorimeter is 22° C. or more and 40° C. or less,

[0013] The melt flow rate measured at a temperature of 190° C. and a load of 2.16 kg is 0.8 g / 10 minutes or more and 8.0 g / 10 minutes or less.

[0014] [2] The wire material according to [1], wherein the polyacetal resin contains 1.0% by mass or more and 6.0% by mass or less of the comonomer unit in all structural units (100% by mass).

[0015] [3] The wire material according to [2], wherein the comonomer unit is an oxyalkylene unit having 2 or more carbon atoms.

[0016] [4] The wire material according to [2], wherein the comonomer unit is at least one oxyalkylene unit selected from the group consisting of oxyethylene, oxypropylene and oxytetramethylene.

[0017] [5] The wire material according to any one of [1] to [4], wherein the wire material has an average diameter of 1 to 3 mm.

[0018] [6] The wire material according to any one of [1] to [5], comprising an inorganic or organic filler.

[0019] [7] A method for manufacturing a three-dimensional object, comprising the steps of: forming the three-dimensional object by a hot melt deposition method using the wire material described in any one of [1] to [6].

[0020] [8] The manufacturing method according to [7], wherein the step of forming the three-dimensional object comprises the following steps:

[0021] A three-dimensional object is formed on a molding table under the temperature conditions shown in the following formula 1:

[0022] Tm2>Ts≥Tc, and Tc>Ta>Tc-100 (Formula 1)

[0023] [In Formula 1, Ts is the temperature of the molding table (°C), Tc is the crystallization temperature of the aforementioned wire (°C), Tm2 is the melting point of the aforementioned wire (°C), and Ta is the ambient temperature of the molding area (°C)]

[0024] Furthermore, the method comprises the following steps:

[0025] After the step of forming the three-dimensional object, the three-dimensional object is peeled off from the surface of the molding table under the temperature condition shown in the following formula 2.

[0026] Tc>Ts (Formula 2)

[0027] [In formula 2, Ts and Tc are the same as in formula 1].

[0028] [9] The manufacturing method according to [7] or [8], wherein the step of forming the aforementioned three-dimensional modeling object includes the following steps: after forming a base layer on a modeling table, forming the three-dimensional modeling object on the base layer.

[0029]

[10] A manufacturing method according to any one of [7] to [9], wherein the three-dimensional object obtained in the step of forming the aforementioned three-dimensional object has two points with a straight-line distance of more than 5 cm on the outer edge of the surface in contact with the modeling table or on the outer edge of the surface in contact with the base layer arranged on the modeling table.

[0030]

[11] The manufacturing method according to any one of [7] to

[10] , wherein the height of the three-dimensional object obtained in the step of forming the three-dimensional object is greater than 5 cm from the molding table.

[0031]

[12] A three-dimensional object formed using the wire material described in any one of [1] to [6].

[0032]

[13] A three-dimensional object, comprising a wire composition for three-dimensional modeling,

[0033] The wire composition for three-dimensional modeling contains a polyacetal resin, and the difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc measured by a differential scanning calorimeter is 22° C. or more and 40° C. or less,

[0034] The melt flow rate measured at a temperature of 190° C. and a load of 2.16 kg is 0.8 g / 10 minutes or more and 8.0 g / 10 minutes or less.

[0035]

[14] A three-dimensional object according to

[12] or

[13] , which has one or more faces, each of which has two points on its outer edge with a linear distance of more than 5 cm.

[0036]

[15] A three-dimensional object according to any one of

[12] to

[14] , wherein the height from one surface is greater than 5 cm.

[0037] According to the present disclosure, a three-dimensional modeling wire material that can be three-dimensionally modeled by a thermal melt deposition method can be provided. According to the present disclosure, a three-dimensional modeled object using the three-dimensional modeling wire material and a method for manufacturing the same can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figures 1A to 1D A schematic diagram showing the flow of a method for producing a three-dimensional object by thermal fusion deposition. DETAILED DESCRIPTION

[0039] Hereinafter, one embodiment of the present disclosure is described in detail, but the scope of the present disclosure is not limited to the one embodiment described herein, and various changes can be made within the scope of the spirit of the present disclosure. In addition, if multiple upper limits and lower limits are recorded for a specific parameter, any upper limit and lower limit can be combined within these upper limits and lower limits to form a suitable numerical range. In addition, the lower limit and / or upper limit of the numerical range recorded in the present disclosure is a numerical value within the numerical range, and can also be replaced by the numerical value shown in the embodiment. The expression "X~Y" indicating a numerical range means "above X and below Y". If the specific description recorded for one embodiment is also applicable to other embodiments, its description can be omitted in other embodiments.

[0040] [Wire for 3D modeling]

[0041] The wire for three-dimensional modeling of the present embodiment (hereinafter, also simply referred to as "wire") contains polyacetal resin, and the difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc measured by a differential scanning calorimeter is 22°C or more and 40°C or less, and the melt flow rate measured at a temperature of 190°C and a load of 2.16kg is 0.8g / 10min or more and 8.0g / 10min or less. According to the wire for three-dimensional modeling of the present embodiment, even when the size of the modeling object is large, three-dimensional modeling can be performed by a hot melt deposition method. As a modeling object of large size, for example: when the surface in contact with the modeling table is rectangular, the surface size is 5cm or more × 5cm or more (or 10cm or more × 10cm or more); when the surface in contact with the modeling table is close to a circle, the diameter is 5cm or more (or 10cm or more); and the height from the modeling table is 5cm or more (or 10cm or more). Modeling objects, etc. Usually, when making a large-sized object, the surface area of ​​the modeling table becomes larger, which may cause uneven temperature inside the modeling table. In addition, it takes longer modeling time than making a small-sized object. In the previous method, when polyacetal resin is used as the main component of the resin, there will be uneven temperature inside the modeling table, or when a certain modeling time is required, in the middle of the modeling process, the base layer of the object (the layer in contact with the modeling table) is sometimes peeled off from the modeling table, and it is difficult to continue modeling in this case. Therefore, in the past, the size of the three-dimensional modeling object formed by the hot melt deposition method using polyacetal resin as the main component of the resin was limited to a few centimeters. According to the three-dimensional modeling wire of this embodiment, even if there is a case where the table temperature is uneven in the surface during modeling and the modeling time is long, it is possible to suppress the peeling of the base layer from the table during the modeling process, so that the three-dimensional modeling object can be stably modeled.

[0042] "Wire" is a solid material used for three-dimensional modeling, generally used as a material for 3D printing. It is a continuous fiber shape with a cross-section perpendicular to the length direction of the wire being circular or nearly circular.

[0043] In one embodiment, the average diameter of the wire is preferably 1 to 3 mm, more preferably 1 to 2.5 mm, and further preferably 1.5 to 2 mm. By setting the average diameter of the wire to 1 to 3 mm, it can be used as a modeling material in a commercially available three-dimensional modeling device. The average diameter of the wire is the arithmetic mean of the values ​​obtained by taking out a 5 m sample and randomly selecting 20 positions, measuring the diameter (or the longest straight line distance in the cross section) using a micrometer to the third decimal place, and rounding the value to the third decimal place.

[0044] In one embodiment, the wire material may be a winding body wound on a core material. By making it into a winding body, it can be easier to install in a 3D printer and easier to shape by a 3D printer.

[0045] (Melting point Tm2 and crystallization temperature Tc of wire)

[0046] The difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc of the wire as measured by a differential scanning calorimeter is 22°C to 40°C. By making the (Tm2-Tc) of the wire 22°C to 40°C, it is possible to easily and stably mold larger sized objects. The (Tm2-Tc) of the wire is more preferably 22°C to 35°C, and further preferably 22°C to 30°C. In one embodiment, the (Tm2-Tc) of the wire may be 22°C to 25°C, or 23°C to 25°C.

[0047] The melting point Tm2 represents the temperature of the peak top of the endothermic peak of the 2ndRUN observed when the wire is heated from 40°C to 200°C (1stRUN) at a heating rate of 20°C / min based on the method of JIS K-7121 (2012), maintained at 200°C for 5 minutes, then cooled to 40°C at a cooling rate of 10°C / min, maintained at 40°C for 5 minutes, and then heated from 40°C to 200°C (2ndRUN) at a heating rate of 10°C / min again.

[0048] The crystallization temperature Tc refers to the temperature of the peak top of the exothermic peak observed when the wire is heated from 40°C to 200°C at a heating rate of 20°C / min (1st RUN) based on the method of JIS K-7121 (2012), maintained at 200°C for 5 minutes, and then cooled to 40°C at a cooling rate of 10°C / min.

[0049] In one embodiment, the melting point Tm2 of the wire may be 160° C. or more and less than 170° C., or 162° C. or more and 165° C. or less. In one embodiment, the melting point Tm2 of the wire may be 163° C., or 164° C., or a range in which the melting point Tm2 is set as the upper limit or lower limit of the above numerical range.

[0050] In one embodiment, the crystallization temperature Tc of the wire may be 130° C. to 145° C., or 135° C. to 143° C. In one embodiment, the crystallization temperature Tc of the wire may be 140° C., or 141° C., or a range in which the upper limit or lower limit is set to the above numerical range.

[0051] When the polyacetal resin is a copolymer, the melting point Tm2 can be adjusted by adjusting the ratio of the comonomer units in the polyacetal resin. For example, the greater the ratio of the comonomer units, the lower the melting point Tm2. The crystallization temperature Tc can also be adjusted by adjusting the ratio of the comonomer units. For example, the greater the ratio of the comonomer units, the lower the crystallization temperature Tc.

[0052] (Melt flow rate (MFR) of wire)

[0053] For the wire, the MFR measured at a temperature of 190°C and a load of 2.16kg is 0.8g / 10 minutes or more and 8.0g / 10 minutes or less, preferably 1.0g / 10 minutes or more and 7.0g / 10 minutes or less, and more preferably 1.2g / 10 minutes or more and 6.0g / 10 minutes or less. When the (Tm2-Tc) of the wire is within the above-specified range, the MFR is 0.8g / 10 minutes or more and 8.0g / 10 minutes or less, and even when making a large-sized object, it is easy to perform three-dimensional molding by the hot melt deposition method. The MFR of the wire is measured under the conditions of a temperature of 190°C and a load of 2.16kg based on ISO 1133-1:2011 (condition D). In one embodiment, the MFR of the wire measured at a temperature of 190°C and a load of 2.16kg can be 1.2, can be 1.6, or can be a range in which it is set to the upper limit or lower limit of the above-mentioned numerical range.

[0054] The MFR is mainly adjusted by the weight average molecular weight (Mw) of the polyacetal resin. For example, the larger the weight average molecular weight (Mw) of the polyacetal resin, the lower the MFR tends to be.

[0055] (Polyacetal resin)

[0056] The polyacetal resin may be a polyacetal homopolymer or a polyacetal copolymer. In one embodiment, from the viewpoint of the balance between mechanical properties and thermal properties, the polyacetal resin preferably comprises a polyacetal copolymer. The molecules of the polyacetal resin may be not only linear, but also branched or cross-linked structures, or known modified polyoxymethylenes into which other organic groups have been introduced.

[0057] A polyacetal homopolymer is a polymer having only oxymethylene units (—CH 2 O—) in its main chain.

[0058] The polyacetal copolymer is a copolymer resin containing an oxymethylene unit (-CH2O-) as a main structural unit and further containing a comonomer unit other than the aforementioned oxymethylene unit. "Main structural unit" means a monomer unit that accounts for more than 50% by mass, preferably 70% by mass or more, in all structural units (100% by mass) constituting the polyacetal copolymer.

[0059] The comonomer units contained in the polyacetal copolymer may be one or more than two. In one embodiment, it is preferred that the comonomer units are oxyalkylene units having a carbon number of 2 or more, preferably a carbon number of 2 or more and 6 or less. By having the comonomer units be oxyalkylene units having a carbon number of 2 or more, it is easy to make thermal stability good. The comonomer units are more preferably at least one oxyalkylene unit selected from oxyethylene, oxypropylene and oxytetramethylene, and are particularly preferably oxyethylene.

[0060] For the ratio of the comonomer unit in the polyacetal copolymer, it is preferably 1.0% by mass or more and 6.0% by mass or less relative to the total structural units (100% by mass) of the polyacetal resin, more preferably 1.5% by mass or more and 5.5% by mass or less, particularly preferably 2.0% by mass or more and 5.0% by mass or less, further preferably 2.2% by mass or more and 5.0% by mass or less, and particularly preferably 2.5% by mass or more and 4.5% by mass or less. By the ratio of the comonomer unit being 1.0% by mass or more and 6.0% by mass or less relative to the total structural units (100% by mass) of the polyacetal copolymer, warping or pores can be further reduced, and it is easier to perform three-dimensional modeling by a hot melt deposition method. In addition, a three-dimensional modeling object with excellent appearance can be produced. As a comonomer unit, when containing an oxyethylene unit, the proportion of the oxyethylene unit in the total comonomer unit (100% by mass) is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less.

[0061] It should be noted that the ratio of the comonomer units in the polyacetal copolymer can be determined by 1Calculation by H-NMR method. For example, a wire material is dissolved in deuterated hexafluoroisopropanol to a concentration of 5 mass % to prepare a sample. 1 The sample is analyzed by H-NMR, and the peak can be calculated by determining the ratio of the integrated ratio of the comonomer unit (for example, the oxyalkylene unit having 2 or more carbon atoms described later) to the integrated ratio of the peak of all monomers of the polyacetal copolymer.

[0062] The polyacetal copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer. From the viewpoint of thermal stability, a random copolymer is preferred.

[0063] The degree of polymerization, degree of branching, and degree of crosslinking of the polyacetal resin can be appropriately adjusted within the range where the MFR of the wire material becomes 0.8 to 8.0 g / 10 minutes.

[0064] The weight average molecular weight (Mw) of the polyacetal resin is not particularly limited as long as it has the effect of the present disclosure, and can be appropriately adjusted within the range of 0.8 to 8.0 g / 10 minutes for the MFR of the wire. In one embodiment, from the perspective of making it easy to make the resulting molded object have good strength, the Mw of the polyacetal resin can be 10,000 or more and 400,000 or less. The weight average molecular weight (Mw) is a value measured by size exclusion chromatography (SEC) (polystyrene conversion).

[0065] The polyacetal resin may include only one kind, or may include a combination of more than two kinds selected from polyacetal homopolymers and polyacetal copolymers. In the case of including a polyacetal copolymer, the type and / or content and / or form (random copolymer, block copolymer, graft copolymer, etc.) of the comonomer may also include different polyacetal copolymers of more than two kinds. In the case of including more than two kinds of polyacetal resins, the blending ratio may be adjusted to meet the difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc of the wire, and the value of MFR.

[0066] The content of the polyacetal resin in the wire is preferably more than 50% by mass, more preferably 60% by mass or more, further preferably 70% by mass or more, and may be 80% by mass or more, 90% by mass or more, or 100% by mass, relative to the total mass of the wire. The content of the polyacetal resin in the resin component constituting the wire is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and may be 100% by mass, relative to the total resin component.

[0067] (Method for producing polyacetal resin)

[0068] The polyacetal resin can be produced by the following method: adding a cyclic trimer or tetramer of formaldehyde (more preferably 1,3,5-trioxane, a cyclic trimer of formaldehyde), and adding a monomer (or a monomer mixture) containing a comonomer as needed, adding an appropriate amount of a molecular weight regulator as needed, and performing bulk polymerization using a cationic polymerization catalyst.

[0069] 1,3,5-trioxane is generally obtained by reacting a formaldehyde aqueous solution in the presence of an acidic catalyst, and is used after being purified by distillation or the like. 1,3,5-trioxane used for polymerization preferably contains as little impurities as possible, such as water, methanol, and formic acid.

[0070] The polymerization apparatus is not particularly limited, and a known apparatus can be used. In addition, any method such as a batch method or a continuous method can be used. The polymerization temperature is preferably maintained at 65 to 135° C. The polymerization catalyst can be deactivated after the polymerization by adding a basic compound or an aqueous solution thereof to the reaction product recovered from the polymerization apparatus or the reaction product in the polymerization apparatus.

[0071] Examples of the cationic polymerization catalyst include lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimony trichloride, phosphorus pentafluoride, antimony pentafluoride, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride dibutyl ether complex, boron trifluoride dioxanate, boron trifluoride acetic anhydride, boron trifluoride triethylamine complex and the like; inorganic and organic acids such as perchloric acid, acetyl perchlorate, tert-butyl perchlorate, glycolic acid, trichloroacetic acid, trifluoroacetic acid, p-toluenesulfonic acid and the like; complex salt compounds such as triethyloxonium tetrafluoroborate, trityl hexafluoroantimonate, allyldiazonium hexafluorophosphate, allyldiazonium tetrafluoroborate and the like; alkyl metal salts such as diethylzinc, triethylaluminum, diethylaluminum chloride and the like; heteropolyacids; isopolyacids and the like. Among them, boron trifluoride complexes such as boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride dibutyl ether complex, boron trifluoride dioxane, boron trifluoride acetic anhydride, and boron trifluoride triethylamine complex are particularly preferred. The catalyst may be diluted in an organic solvent or the like before use.

[0072] As the molecular weight modifier, linear formaldehyde compounds can be mentioned. As the linear formaldehyde compounds, for example, methylal, acetal, dibutoxymethane, bis(methoxymethyl)ether, bis(ethoxymethyl)ether, bis(butoxymethyl)ether, etc. can be mentioned. Among them, at least one selected from the group consisting of methylal, acetal and dibutoxymethane is preferred.

[0073] As the alkaline compound used to neutralize the polymerization catalyst for deactivation, ammonia; amines such as triethylamine, tributylamine, triethanolamine, and tributanolamine; hydroxides of alkali metals and alkaline earth metals; and other known catalyst deactivators can be used. In addition, after the polymerization reaction is completed, it is preferred to quickly add the aqueous solution to the reaction product to deactivate it. After the polymerization method and the deactivation method, washing, separation and recovery of unreacted monomers, drying, etc. can be further performed according to conventionally known methods as needed to obtain a polyacetal resin.

[0074] It should be noted that, as required, various stabilizers can be mixed to perform stabilization treatments such as decomposition removal or sealing of the unstable terminal portion of the polyacetal resin. As stabilizers, conventionally known antioxidants, heat stabilizers, etc. can be used. For example, hindered phenol compounds, nitrogen-containing compounds, hydroxides of alkali metals or alkaline earth metals, inorganic salts, carboxylates, etc., can be used alone or in combination.

[0075] It should be noted that, within the scope that does not hinder the effects of the present disclosure, one or more general additives can be added to the polyacetal resin as needed, such as colorants such as dyes and pigments, lubricants, crystal nucleating agents, release agents, antistatic agents, surfactants or organic polymer materials.

[0076] (Other ingredients)

[0077] The wire material may also contain other components as required. As other components, fibrous, powdery, plate-like inorganic or organic fillers, thermoplastic resins other than polyacetal resins (other thermoplastic resins), etc. may be cited. As required, the wire material may add one or more general additives to the thermoplastic resin, such as weathering (light) stabilizers, dyes, pigments and other colorants, lubricants, nucleating agents, release agents, antistatic agents, surfactants, etc.

[0078] (Inorganic or organic fillers)

[0079] In one embodiment, the wire may contain an inorganic or organic filler. As an inorganic or organic filler, for example: a powdery filler or a plate-like filler having an average particle size of 2nm to 400μm, preferably 20nm to 100μm; an average fiber length of 0.1 to 600μm, preferably 1 to 300μm, an average fiber diameter of 0.001 to 20μm, preferably 0.01 to 15μm, and a fibrous filler. By including an inorganic or organic filler, it is easier to improve the strength of the resulting three-dimensional object. It should be noted that the average particle size of the inorganic or organic filler represents the particle size D50 when the cumulative frequency in the volume-based arithmetic mean particle size by the laser diffraction / scattering particle size distribution measurement method becomes 50%. The average particle size can be measured using, for example, a laser diffraction / scattering particle size distribution measuring device (manufactured by Kuba Seisakusho Co., Ltd., product name: LA-960). The average fiber length can be obtained by calculating the arithmetic mean of the values ​​obtained by measuring 500 fibrous fillers using an image measuring device (manufactured by NIRECO Co., Ltd., product name: LUZEXFS). The average fiber diameter can be obtained by calculating the arithmetic mean of the values ​​obtained by measuring the longest straight line distance in a cross section perpendicular to the longitudinal direction of 500 fibrous fillers using an image measuring device (manufactured by NIRECO Co., Ltd., product name: LUZEXFS).

[0080] As the powdery filler, for example, carbon black, graphite, silicon dioxide, quartz powder, glass beads, glass balls, glass powder, silicates such as calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, aluminum oxide, metal carbonates such as calcium carbonate, magnesium carbonate, metal sulfates such as calcium sulfate, barium sulfate, other ferrites, silicon carbide, silicon nitride, boron nitride, various metal powders, etc. The powdery filler can be used alone or in combination of two or more.

[0081] As fibrous fillers, for example, glass fiber, milled glass fiber, carbon fiber, asbestos fiber, silica fiber, silica·alumina fiber, alumina fiber, zirconium oxide fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, silicate fiber such as wollastonite, magnesium sulfate fiber, aluminum borate fiber, and inorganic fibrous substances such as fibrous materials of metals such as stainless steel, aluminum, titanium, copper, and brass can be listed. A particularly typical fibrous filler is glass fiber. High melting point organic fibrous substances such as polyamide, fluororesin, polyester resin, and acrylic resin can also be used. These fibrous fillers can be used alone or in combination of two or more.

[0082] Examples of the plate-like filler include mica, glass flakes, talc, and various metal foils. The plate-like filler may be used alone or in combination of two or more.

[0083] When the wire material contains an inorganic or organic filler, the content is set to satisfy the difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc of the wire material and the MFR within the above-mentioned range. The content of the inorganic or organic filler may also be, for example, 0 to 50% by mass relative to the total mass of the wire material.

[0084] (Other thermoplastic resins)

[0085] In one embodiment, the wire material may include other thermoplastic resins other than polyacetal resin. As other thermoplastic resins, for example, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, etc. can be cited. These can be used alone or in combination of two or more.

[0086] When the wire material includes other thermoplastic resins, the blending amount thereof is set to satisfy the difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc of the wire material, and the MFR is within the above-mentioned range. The content of other thermoplastic resins can be, for example, 0 to 15 parts by mass, or 1 to 10 parts by mass relative to 100 parts by mass of the polyacetal resin.

[0087] [Method for manufacturing wire rod]

[0088] The polyacetal resin obtained by the above production method is extruded by an extruder together with other components that may be contained as needed, and the extruded strand is cooled and solidified, and then wound by a winder at a winding speed that gives the wire a desired diameter to produce a wire.

[0089] In the manufacturing method of the wire, one polyacetal resin can be used alone, or two or more selected from polyacetal homopolymers and polyacetal copolymers can be used in combination. When using a polyacetal copolymer, two or more polyacetal copolymers with different types and / or contents and / or forms (random copolymers, block copolymers, graft copolymers, etc.) of comonomers can also be used. When using two or more polyacetal resins, the blending ratio can be adjusted to meet the difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc of the wire, and the value of MFR.

[0090] [Method for producing three-dimensional object]

[0091] The manufacturing method of the three-dimensional modeling object of this embodiment includes the following steps: using the above-mentioned three-dimensional modeling wire to form a three-dimensional modeling object by a hot melt deposition method. In one embodiment, the step of forming the three-dimensional modeling object includes the following steps: spraying the melt of the above-mentioned three-dimensional modeling wire onto a modeling table. In one embodiment, the modeling table can be provided in a 3D printer.

[0092] In one embodiment, preferably, the step of forming a three-dimensional modeled object (hereinafter also referred to as “first step”) includes the step of forming the three-dimensional modeled object on a modeling table under the temperature condition represented by the following formula 1.

[0093] Tm2>Ts≥Tc, and Tc>Ta>Tc-100 (Formula 1)

[0094] [In Formula 1, Ts is the temperature of the molding table (°C), Tc is the crystallization temperature of the wire (°C), Tm2 is the melting point of the wire (°C), and Ta is the ambient temperature of the molding area (°C)]

[0095] Furthermore, the method includes the step of peeling the three-dimensional modeled object from the surface of the modeling table under the temperature condition represented by the following formula 2 after the step of forming the three-dimensional modeled object (hereinafter also referred to as "second step").

[0096] Tc>Ts (Formula 2)

[0097] [In formula 2, Ts and Tc are the same as in formula 1].

[0098] The "modeling area" refers to a space on a modeling table where a three-dimensional model can be formed. In one embodiment, the modeling area is preferably a chamber that forms a closed space in order to facilitate temperature regulation.

[0099] The ambient temperature (Ta) of the molding area and the molding table temperature (Ts) can be adjusted by increasing or decreasing the settings on the hot melt deposition 3D printer. However, the ambient temperature (Ta) of the molding area and the molding table temperature (Ts) are not the set values ​​of the 3D printer operation. Instead, they represent the actual measured values ​​of the molding table temperature and the ambient temperature of the molding area under certain set conditions.

[0100] The method for measuring the melting point Tm2 and the crystallization temperature Tc of the wire is the same as that described for the wire.

[0101] In the first step, by setting the various temperatures during the wire stacking to the range defined by Formula 1, the warping of the deposited material caused by the temperature drop during stacking can be further suppressed, and the deposited material can be firmly fixed on the molding table. Therefore, it is easier to manufacture a large-sized three-dimensional molded object.

[0102] In the second step, by setting the temperature of the molding table after molding to the range defined by Formula 2, the formed three-dimensional molded object can be easily peeled off from the molding table.

[0103] Fig. 1 schematically shows the flow of a method for producing a three-dimensional object by a thermal melt deposition method. Fig. 1 (A) to Fig. 1 (C) show the first step, and Fig. 1 (D) shows the second step.

[0104] First, as required, the temperature Ts of the modeling table 1 and the ambient temperature Ta of the modeling zone in the 3D printer of the hot melt deposition method are set to a predetermined temperature (e.g., a temperature satisfying the above formula 1) (Fig. 1 (A)). In one embodiment, for example, when the melting point Tm2 of the polyacetal resin is set to 163.9°C and the crystallization temperature Tc is set to 140.5°C, the temperature of the modeling table 1 is preferably set to 141°C or more and less than 163.9°C, and the ambient temperature of the modeling zone is preferably set to more than 40°C and less than 140°C.

[0105] Next, the wire for three-dimensional modeling is melted and ejected from the ejection nozzle 2 onto the modeling table 1. The ejection nozzle 2 is scanned above the modeling table 1, and the molten wire is ejected from the ejection nozzle 2, so that the base layer 4 can be formed (Figure 1 (B)). Furthermore, the ejection nozzle 2 is scanned above the base layer 4, and the molten wire is ejected from the ejection nozzle 2, so that the structure 5 is formed on the base layer 4 (Figure 1 (C)). More specifically, based on the three-dimensional data of the structure 5 to be formed, the shape corresponding to the cross-section of the structure 5 is sequentially accumulated to form the structure 5. In the formation process of the structure 5, air is ejected from the air guide 3 located near the ejection nozzle 2, so that the accumulated modeling material can be cooled and solidified. After the formation of the structure 5 is completed, the temperature of the modeling table 1 can be lowered as needed, and the temperature of the base layer can be lowered to a temperature lower than the crystallization temperature of the wire. Thus, the base layer 4 is crystallized, the adhesion of the base layer 4 to the modeling table 1 is reduced, and the three-dimensional modeled object 6 composed of the base layer 4 and the structural portion 5 can be easily peeled off from the modeling table 1 ((D) in FIG. 1 ). In one embodiment, after the formation of the structural portion 5, the temperature of the modeling table 1 can be set to a temperature that satisfies the above formula 2. In one embodiment, for example, when the crystallization temperature Tc of the polyacetal resin is set to 140.5°C, after the formation of the structural portion 5, the temperature of the modeling table 1 is preferably lowered to less than 140°C. The peeled structural portion 5 (or the base layer 4 and the structural portion 5) can be obtained as a three-dimensional modeled object 6. Thereafter, the base layer 4 is removed by cutting, grinding, etc. as needed.

[0106] It should be noted that the base layer 4 is a base formed under the structure 5, and can be formed with a larger area than the structure 5 and / or without gaps or gaps. By forming the base layer 4, it is possible to further prevent the structure 5 from peeling off from the molding platform when the molding time is long.

[0107] In one embodiment, the step of forming the three-dimensional object may include the following steps: after forming a base layer on the aforementioned modeling table, forming the three-dimensional object on the base layer.

[0108] The above three-dimensional object manufacturing method can suppress the base layer from peeling off from the stage during the molding process even when the molding time is long, so the base layer 4 does not necessarily need to be formed. When the base layer 4 is not formed, the structure 5 can be directly formed on the molding stage 1.

[0109] In one embodiment, in order to form a large-sized shaped object, the size of the shaped table can be a side length (or diameter) of more than 5 cm, more than 10 cm, 15 to 100 cm, or 20 to 90 cm.

[0110] In one embodiment, the three-dimensional object obtained in the step of forming the three-dimensional object may have two points with a linear distance of 5 cm or more on the outer edge of the surface in contact with the molding table or the outer edge of the surface in contact with the base layer provided on the molding table, or may have two points with a linear distance of 10 cm or more. By forming a three-dimensional object having a surface with two points with a linear distance of 5 cm or more (or 10 cm or more) on the outer edge of the surface in contact with the molding table or the outer edge of the surface in contact with the base layer provided on the molding table, even a three-dimensional object of a larger size than before can be three-dimensionally molded by the hot melt deposition method.

[0111] In another embodiment, the three-dimensional object obtained in the step of forming a three-dimensional object has a polygonal shape in which the surface in contact with the modeling table or the surface in contact with the base layer disposed on the modeling table has a side length of at least one of 5 cm or more, or at least 10 cm or more. In another embodiment, the three-dimensional object obtained in the step of forming a three-dimensional object has a circular shape in which the surface in contact with the modeling table or the surface in contact with the base layer disposed on the modeling table has a diameter of at least 5 cm or more, or at least 10 cm or more.

[0112] In one embodiment, the three-dimensional object obtained in the step of forming the three-dimensional object may have a height of 5 cm or more from the molding table, or may have a height of 10 cm or more. Even if the height of the three-dimensional object is larger than the conventional size, such as 5 cm or more from the molding table, the three-dimensional molding may be performed by the hot melt deposition method.

[0113] [Three-dimensional objects]

[0114] The three-dimensional object of this embodiment is a three-dimensional object formed using the above-mentioned three-dimensional modeling wire. In one embodiment, the three-dimensional object can be a three-dimensional object formed by the above-mentioned three-dimensional modeling wire through a hot melt deposition method. The three-dimensional object formed using the three-dimensional modeling wire can be judged by confirming the modeling line (drawing line) and the deposition mark when observing the surface of the three-dimensional object visually or with a stereoscopic microscope. The thickness of the modeling line (drawing line) is not particularly limited, and can be, for example, 100 to 1000 μm.

[0115] In one embodiment, the three-dimensional shaped object can be a three-dimensional shaped object comprising a wire composition for three-dimensional modeling, the wire composition for three-dimensional modeling comprises a polyacetal resin, and the difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc measured by a differential scanning calorimeter is greater than 22°C and less than 40°C, and the melt flow rate measured at a temperature of 190°C and a load of 2.16 kg is greater than 0.8g / 10min and less than 8.0g / 10min.

[0116] The "wire composition for three-dimensional modeling" refers to a composition comprising the components constituting the above-mentioned wire for three-dimensional modeling. Since the wire composition for three-dimensional modeling comprises a polyacetal resin, it is sometimes referred to as a "polyacetal resin composition" below. In one embodiment, when a three-dimensional modeling object comprising the wire composition for three-dimensional modeling is observed visually or with a stereomicroscope, modeling lines (drawing lines) and accumulation marks can be confirmed.

[0117] In one embodiment, the three-dimensional object has one or more faces with two points on the outer edge having a linear distance of 5 cm or more, or one or more faces with two points on the outer edge having a linear distance of 10 cm or more. In one embodiment, the height of the three-dimensional object from one face may be 5 cm or more, or 10 cm or more. In one embodiment, the three-dimensional object may have two points on the outer edge having a linear distance of 5 cm or more, or two points on the outer edge having a linear distance of 10 cm or more.

[0118] In another embodiment, the three-dimensional object may have one or more polygonal faces, and the length of one or more sides of the polygonal faces may be greater than 5 cm, or greater than 10 cm. In another embodiment, the three-dimensional object may have one or more circular faces, and the diameter of the circular faces may be greater than 5 cm, or greater than 10 cm.

[0119] Example

[0120] Examples are shown below to further illustrate the present disclosure, but the interpretation of the present disclosure is not limited to these examples.

[0121] [Manufacturing Example 1] (Manufacturing of polyacetal resin)

[0122] The polymerization was carried out using a continuous mixing reactor, which was provided with a jacket for passing a heat carrier (or a refrigerant) on the outside and was composed of a paddle-attached rotating shaft having a cross section in the shape of two partially overlapping circles. Specifically, while the two rotating shafts with paddles were rotated at 150 rpm, 1,3,5-trioxane and a comonomer (1,3-dioxolane) were added to the reactor in the proportions shown in Table 1. Furthermore, methylal was added as a molecular weight regulator in the proportions shown in Table 1. Next, a catalyst mixture in which boron trifluoride gas as a catalyst was mixed in a manner of 0.005% by mass in terms of boron trifluoride relative to 1,3,5-trioxane was continuously added and supplied to carry out bulk polymerization. After the polymerization was completed, while the reaction product discharged from the reactor was quickly passed through a crusher, an 80°C aqueous solution containing 0.1% by mass of triethylamine was added to deactivate the catalyst. And, after separation, washing, and drying, a crude polyacetal resin was obtained.

[0123] Next, 4 parts by mass of a 5% by mass aqueous solution of triethylamine and 0.03 parts by mass of pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant) were added to 100 parts by mass of the crude polyacetal resin, and melt-kneaded at 210° C. using a twin-screw extruder to remove unstable portions of the crude polyacetal resin. 0.3 parts by mass of pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 0.15 parts by mass of melamine were further added as stabilizers to 100 parts by mass of the polyacetal resin obtained by the above method, and melt-kneaded at 210° C. using a twin-screw extruder to obtain a pelletized polyacetal resin.

[0124] The amount of the comonomer relative to the total monomers (100% by mass) of the obtained polyacetal resin was 5.9% by mass. 1 The ratio of the comonomer unit (calculated as oxyethylene unit) to the total structural units (100% by mass) of the polyacetal resin was 3.5% by mass as calculated by H-NMR method. The detailed calculation method of the comonomer unit will be described later.

[0125] [Production Example 2]

[0126] A pelletized polyacetal resin was obtained in the same manner as in Production Example 1 except that the feed amounts of 1,3,5-trioxane, comonomer (1,3-dioxolane) and methylal were set to the ratios shown in Table 1. The ratio of the comonomer unit (in terms of oxyethylene unit) relative to the total structural units (100% by mass) of the polyacetal resin was measured by the following method. The results are shown in Table 1.

[0127] (Comonomer unit)

[0128] The obtained pelletized polyacetal resin was cut into small pieces with scissors to make it easily soluble in a solvent, and the pieces were dissolved in deuterated hexafluoroisopropanol to a concentration of 5 mass %, thereby preparing a sample. 1 The sample was analyzed by H-NMR (manufactured by Bruker, product name: AvanceIII 400, magnetic field strength: 400 MHz, reference substance: tetramethylsilane, temperature: 27°C, accumulation number: 128 times) to obtain the ratio of the integral rate of the copolymerized monomer unit (ethylene oxide) to the integral rate of the peak of all monomers of the polyacetal resin.

[0129] [Example 1]

[0130] Using the pelletized polyacetal resin obtained in Production Example 1, a wire material having an average diameter of 1.75 mm was prepared by the following method.

[0131] The polyacetal resin pellets were put into a table-type extruder (APEX JAPAN, AS-1) and extruded at a drum temperature of 200°C and a screw speed of 40 rpm. The extruded strands were cooled and solidified by water, and then wound with a wire winding machine (FILABOT, Spooler) at a winding speed such that the wire diameter became 1.75 mm ± 0.1 mm to obtain a wire formed of polyacetal resin.

[0132] The MFR, melting point Tm2, ​​crystallization temperature Tc, and average diameter of the obtained wire rod were measured by the following method. The values ​​of MFR, melting point Tm2, ​​and crystallization temperature Tc are shown in Table 1.

[0133] (Melt Flow Rate (MFR))

[0134] The measurement was performed according to ISO 1133 (Condition D) at a temperature of 190°C and a load of 2.16 kg.

[0135] (Melting point Tm2, ​​crystallization temperature Tc)

[0136] Using a differential scanning calorimeter (manufactured by Parkin Elmer, product name: DSC8500), according to JIS K-7121 (2012), after heating from 40°C to 200°C (1st RUN) at a heating rate of 20°C / min, the temperature of the peak top of the exothermic peak observed when the sample was kept at 200°C for 5 minutes and then cooled to 40°C at a cooling rate of 10°C / min was measured as the crystallization temperature Tc. Thereafter, the sample was kept at 40°C for 5 minutes and heated again from 40°C to 200°C at a heating rate of 10°C / min, and the temperature of the peak top of the endothermic peak of the 2nd RUN observed was measured as the melting point Tm2.

[0137] (Measurement of average wire diameter)

[0138] A 5-meter sample was taken from the obtained wire rod and 20 locations were randomly selected and the diameter was measured to the third decimal place using a micrometer (manufactured by Mitutoyo Co., Ltd., product name: ABSOLUTE). Then, the third decimal place of the average value was rounded off to the average diameter of the wire rod.

[0139] Next, the obtained wire material is used to produce a three-dimensional object in the following method.

[0140] (1st step)

[0141] The prepared wire is placed in a 3D printer with hot melt deposition (manufactured by INTAMSYS, trade name: FUNMAT HT Enhanced) to form three kinds of three-dimensional objects (80mm×10mm×4mm test piece A, 20mm×20mm×20mm right hexahedron, and 50mm×50mm×50mm right hexahedron). Specifically, first, under the temperature conditions shown below, a sheet-like base layer with an edge size of 1cm is formed for the bottom surface shape of each of the above-mentioned objects, and then the structural part is formed under the same temperature conditions. It should be noted that in the 3D printer, the inner diameter of the nozzle that ejects the wire is 0.4mm, the stacking spacing is set to 0.2mm, and the drawing speed of the structural part is set to 30mm / s.

[0142] <Temperature Conditions of Step 1>

[0143] Temperature of the spray nozzle: 205℃

[0144] Styling table temperature (Ts): 155°C

[0145] Ambient temperature of the molding area (Ta): 94°C

[0146] <Temperature Conditions of Step 2>

[0147] Styling table temperature (Ts): 120℃

[0148] In Example 1, the modeling material (molten wire) can be deposited without any problem until the end with the three-dimensional modeled object fixed on the modeling table, thereby manufacturing all three types of three-dimensional modeled objects.

[0149] (Second step)

[0150] After the first step, the temperature of the modeling table was lowered to 120°C, and the three-dimensional modeling object was peeled off from the surface of the modeling table. At this time, the base layer of all three types of three-dimensional modeling objects was completely white, and the adhesion to the surface of the modeling table was reduced. Even without special peeling work, the three-dimensional modeling object can be naturally peeled off from the modeling table.

[0151] [Example 2]

[0152] A pelletized polyacetal resin composition was obtained in the same manner as in Example 1 except that 100 parts by mass of the pelletized polyacetal resin obtained in Manufacturing Example 1 and 10 parts by mass of glass fiber (manufactured by Nippon Electric Glass Co., Ltd., Chopped Strand ECS 03T-651G, fiber diameter: 9 μm, fiber length: 3 mm) were melt-kneaded at 210° C. using a twin-screw extruder. A wire having an average diameter of 1.75 mm was prepared from the obtained polyacetal resin composition in the same manner as in Example 1. The MFR, melting point Tm2, ​​crystallization temperature Tc, and average diameter of the obtained wire were measured in the same manner as in Example 1. The values ​​of MFR, melting point Tm2, ​​and crystallization temperature Tc are shown in Table 1.

[0153] Next, three types of three-dimensional objects were formed under the same temperature conditions and manufacturing method as in Example 1. In Example 2, for all three types of three-dimensional objects, the objects were fixed on the modeling table until the modeling materials were piled up without any problems to produce the three-dimensional objects. In addition, after the modeling, by lowering the table temperature, the three-dimensional objects could be naturally peeled off from the modeling table as in Example 1.

[0154] [Comparative Example 1]

[0155] A wire having an average diameter of 1.75 mm was prepared in the same manner as in Example 1 except that the pelletized polyacetal resin obtained in Production Example 2 was used. The MFR, melting point Tm2, ​​crystallization temperature Tc, and average diameter of the obtained wire were measured in the same manner as in Example 1. The values ​​of MFR, melting point Tm2, ​​and crystallization temperature Tc are shown in Table 1.

[0156] Next, three kinds of three-dimensional objects were formed under the same temperature conditions and manufacturing method as in Example 1. In Comparative Example 1, although three-dimensional objects could be formed for the 80 mm × 10 mm × 4 mm test piece A and the 20 mm × 20 mm × 20 mm right hexahedron, the 50 mm × 50 mm × 50 mm right hexahedron peeled off from the molding table during the formation of the base layer, and the molding of the first step could not be completed, and a three-dimensional object could not be formed.

[0157] [Table 1]

[0158]

[0159] ○: A three-dimensional object is obtained.

[0160] ×: The molded object peeled off from the molding table during the formation of the base layer, and the molding of the first step could not be completed.

[0161] Industrial Applicability

[0162] Since the wire material disclosed in the present invention can be three-dimensionally molded by a hot melt deposition method, it is industrially applicable as a wire material for a 3D printer.

[0163] Description of Reference Numerals

[0164] 1: Modeling table

[0165] 2: Spray nozzle

[0166] 3: Airway

[0167] 4: Basal layer

[0168] 5:Structure

[0169] 6: Three-dimensional objects

Claims

1. A wire material for three-dimensional modeling, comprising a polyacetal resin, and The difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc measured by a differential scanning calorimeter is 22° C. or more and 40° C. or less, The melt flow rate measured at a temperature of 190° C. and a load of 2.16 kg is 0.8 g / 10 minutes or more and 8.0 g / 10 minutes or less.

2. The wire according to claim 1, wherein The polyacetal resin contains 1.0 mass % or more and 6.0 mass % or less of the comonomer unit in all the structural units (100 mass %).

3. The wire according to claim 2, wherein: The comonomer unit is an oxyalkylene unit having 2 or more carbon atoms.

4. The wire according to claim 2, wherein: The comonomer unit is at least one oxyalkylene unit selected from the group consisting of oxyethylene, oxypropylene and oxytetramethylene.

5. The wire material according to any one of claims 1 to 4, which has an average diameter of 1 to 3 mm.

6. The wire material according to any one of claims 1 to 4, comprising an inorganic or organic filler.

7. A method for manufacturing a three-dimensional object, comprising the following steps: using the wire material according to claim 1 to form a three-dimensional object by a hot melt deposition method.

8. The manufacturing method according to claim 7, wherein: The steps of forming the three-dimensional object include the following steps: A three-dimensional object is formed on a molding table under the temperature conditions shown in the following formula 1: Tm2>Ts≥Tc, and Tc>Ta>Tc-100 (Formula 1) In formula 1, Ts is the temperature of the molding table (°C), Tc is the crystallization temperature of the wire (°C), Tm2 is the melting point of the wire (°C), and Ta is the ambient temperature of the molding area (°C); Furthermore, the method comprises the following steps: After the step of forming the three-dimensional object, the three-dimensional object is peeled off from the surface of the molding table under the temperature condition represented by the following formula 2, Tc>Ts (Formula 2) In Formula 2, Ts and Tc are the same as in Formula 1.

9. The manufacturing method according to claim 7 or 8, wherein: The step of forming the three-dimensional modeling object comprises the following steps: after forming a base layer on a modeling table, forming the three-dimensional modeling object on the base layer.

10. The manufacturing method according to claim 7 or 8, wherein: The three-dimensional object obtained in the step of forming the three-dimensional object has two points with a linear distance of 5 cm or more on the outer edge of the surface in contact with the modeling table or the outer edge of the surface in contact with the base layer set on the modeling table.

11. The manufacturing method according to claim 7 or 8, wherein: In the step of forming the three-dimensional object, the height of the three-dimensional object obtained from the modeling table is 5 cm or more.

12. A three-dimensional object formed by using the wire material according to claim 1.

13. A three-dimensional modeled object, comprising a wire composition for three-dimensional modeling, The wire composition for three-dimensional modeling comprises a polyacetal resin, and the difference (Tm2-Tc) between the melting point Tm2 and the crystallization temperature Tc measured by a differential scanning calorimeter is 22° C. or more and 40° C. or less, The melt flow rate measured at a temperature of 190° C. and a load of 2.16 kg is 0.8 g / 10 minutes or more and 8.0 g / 10 minutes or less.

14. The three-dimensional object according to claim 12 or 13, which has one or more surfaces, and the surface has two points on the outer edge with a linear distance of 5 cm or more.

15. The three-dimensional object according to claim 12 or 13, wherein the height from one surface is 5 cm or more.

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