Three-dimensional printing filament, wound body, method for producing three-dimensional printing filament, and method for producing molded product

Abstract

A novel 3D printing filament, a wound body, a method for producing the 3D printing filament, and a method for producing a molded product are provided. A 3D printing filament comprises continuous reinforcing fibers impregnated with a thermosetting resin composition containing a thermosetting resin and is solid at 25°C.

Description

Technical Field

[0001] The present invention relates to a filament for three-dimensional printing. More specifically, it relates to a filament for three-dimensional printing used in the manufacture of a three-dimensional object using three-dimensional printing. In addition, the present invention relates to a wound body formed by winding the filament for three-dimensional printing around a core material, a method for manufacturing the filament for three-dimensional printing, and a method for manufacturing a molded product. Background Art

[0002] A 3D printer is a type of rapid prototyping (3D modeling machine) that uses 3D data such as CAD and CG created on a computer as a design drawing to produce a three-dimensional object made of plastic or the like.

[0003] As one of the three-dimensional printing methods, a method using material extrusion deposition is known. The principle of material extrusion deposition is to melt the forming material by heat, etc. to fluidize it, and then eject it from the head nozzle to a specified position based on the three-dimensional data, and repeat this operation to stack it to form a three-dimensional shape.

[0004] In the case of the material extrusion deposition method, a filament-shaped material in which continuous reinforcing fibers are impregnated with a thermoplastic resin is used as a molding material (see Patent Documents 1 and 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application No. 2016-518267

[0008] Patent Document 2: Japanese Patent Application No. 2016-520459 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] In view of the ease of three-dimensional shaping by three-dimensional printing, thermoplastic resins have been conventionally used as materials for three-dimensional printing filaments, and three-dimensional printing filaments using thermosetting resins have not been known to date.

[0011] Therefore, an object of the present invention is to provide a novel filament for three-dimensional printing, a wound body, a method for producing the filament for three-dimensional printing, and a method for producing a molded product.

[0012] Solutions for solving problems

[0013] The present invention provides the following.

[0014] <1> A filament for three-dimensional printing, wherein a thermosetting resin composition containing a thermosetting resin is impregnated in continuous reinforcing fibers and is solid at 25°C.

[0015] <2> according to <1> The filament for three-dimensional printing has a viscosity value of 0 to 3 kPa measured at 23° C. and a probe pressing load of 20 kPa.

[0016] <3> according to <1> or <2> The filament for three-dimensional printing has a viscosity value of 3 kPa or more measured at any temperature of 40 to 250° C. with a probe pressing load of 20 kPa.

[0017] <4> according to <1> ~ <3> The filament for three-dimensional printing according to any one of the preceding claims, wherein the volume content of the continuous reinforcing fibers in the filament for three-dimensional printing is 10 to 80% by volume.

[0018] <5> according to <1> ~ <4> The filament for three-dimensional printing described above, wherein the number of single fibers of the continuous reinforcing fibers is 100 or more.

[0019] <6> according to <1> ~ <5> The filament for three-dimensional printing described in any one of the above, wherein the continuous reinforcing fiber is at least one selected from carbon fiber, glass fiber and aramid fiber.

[0020] <7> according to <1> ~ <6> The filament for three-dimensional printing described in any one of the above, wherein the weight average molecular weight of the thermosetting resin is 200 to 50,000.

[0021] <8> according to <1> ~ <7> The filament for three-dimensional printing described in any one of the above, wherein the softening point of the thermosetting resin is 40 to 250°C.

[0022] <9> according to <1> ~ <8> The filament for three-dimensional printing described above, wherein the thermosetting resin is solid at 25°C.

[0023] <10> according to <1> ~ <9> The filament for three-dimensional printing described in any one of the above, wherein the thermosetting resin contains at least one selected from cyanate resin, bismaleimide triazine resin, phenolic resin, benzoxazine resin, epoxy resin, unsaturated polyester resin and diallyl phthalate resin.

[0024] <11> according to <1> ~ <10> The three-dimensional printing filament described in any one of the preceding claims, wherein a cross-section in a direction perpendicular to a longitudinal direction of the three-dimensional printing filament has a circular shape, a flat shape, or an elliptical shape.

[0025] <12> A roll-up body, which is <1> ~ <11> The three-dimensional printing filament described in any one of the above is wound around a core material.

[0026] <13> A method for manufacturing filament for three-dimensional printing, comprising: <1> ~ <11> The method for producing a filament for three-dimensional printing described in any one of the preceding claims comprises the step of impregnating continuous reinforcing fibers with a thermosetting resin composition containing a thermosetting resin.

[0027] <14> A method for manufacturing a molded product, wherein a nozzle of a 3D printer is <1> ~ <11> The three-dimensional printing filament described in any one of the above is ejected onto a substrate to produce a three-dimensional object, and the three-dimensional object is heated.

[0028] Effects of the Invention

[0029] According to the present invention, a novel filament for three-dimensional printing, a wound body, a method for producing the filament for three-dimensional printing, and a method for producing a molded product can be provided. DETAILED DESCRIPTION

[0030] The content of the present invention is described in detail below. The description of the constituent conditions described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range represented by "~" refers to the range including the numerical values ​​recorded before and after "~" as the lower limit and upper limit.

[0031] <3D printing filament>

[0032] The filament for three-dimensional printing of the present invention is a material which is solid at 25° C. in which continuous reinforcing fibers are impregnated with a thermosetting resin composition containing a thermosetting resin.

[0033] The 3D printing filament of the present invention is the so-called 3D printing ink ejected from the nozzle of the 3D printer. The 3D printing filament of the present invention contains a thermosetting resin, so that a molded product having excellent mechanical properties such as strength can be manufactured using 3D printing. In addition, the 3D printing filament of the present invention is produced by appropriately promoting the curing reaction, so that the stickiness at room temperature (e.g., 20 to 30°C) can be reduced. Therefore, contamination (e.g., conveying rollers, etc.) and nozzle clogging in the 3D printer can also be suppressed. Therefore, the maintenance work of the 3D printer can be simplified.

[0034] The filament for three-dimensional printing of the present invention preferably has a viscosity value (T 23 ) is 0 to 3 kPa, more preferably 0 to 2 kPa, and further preferably 0 to 1 kPa. If the viscosity value at 23°C is within the above range, the stickiness at room temperature can be reduced, and contamination and nozzle clogging in the 3D printer can be more effectively suppressed. Furthermore, it can also be expected that the filaments do not need to be wound with process paper.

[0035] The viscosity of the filament for three-dimensional printing of the present invention measured at 35° C. and a probe pressing load of 20 kPa is preferably 0 to 3 kPa, more preferably 0 to 2 kPa, and even more preferably 0 to 1 kPa. If the viscosity at 35° C. is within the above range, the storage property is excellent.

[0036] The filament for three-dimensional printing of the present invention preferably has a viscosity value of 3 kPa or more, more preferably 4 kPa or more, and further preferably 5 kPa or more, at any temperature of 40 to 250 ° C, measured with a probe pressing load of 20 kPa. According to this method, it can be expected that the printability can be improved and the interlayer strength of the shape can be improved. In addition, from the reason that the printability and the interlayer strength of the shape can be further improved, the filament for three-dimensional printing of the present invention is preferably 3 kPa or more, more preferably 4 kPa or more, and further preferably 5 kPa or more, at 100 ° C or 150 ° C (preferably 100 ° C) The viscosity value measured with a probe pressing load of 20 kPa is more than 3 kPa, more preferably 4 kPa or more, and further preferably 5 kPa or more.

[0037] It should be noted that in this specification, the viscosity value of the filament for three-dimensional printing is the peak value of the adhesion measured by the probe viscosity test method. The probe viscosity test method refers to a method of measuring the force required for peeling at a constant speed after pressing a measuring sub (probe) with a constant contact area with a constant load for a constant time. The peak adhesion refers to the maximum value of the resistance generated when the contact surface between the probe and the sample is peeled off, which is the value obtained by the probe viscosity test under the conditions described below.

[0038] (Test conditions)

[0039] Probe diameter: 10mm

[0040] Probe pressing load: 20kPa

[0041] Probe pressing time: 30 seconds

[0042] Probe pressing speed: 30mm / min

[0043] Probe lifting speed: 10mm / min

[0044] (step)

[0045] 1) The paralleled filaments are fixed to a sample stand adjusted to a predetermined temperature. If the filament size is smaller than the probe diameter, multiple filaments are paralleled without gaps to a size of 10 mm x 10 mm and fixed to the sample stand.

[0046] 2) The probe was pressed against the filament of the sample stage at a pressing speed of 30 mm / min, a load of 20 kPa was applied, and the pressing was performed for 30 seconds.

[0047] 3) The probe is lifted at a lifting speed of 10 mm / min.

[0048] 4) The maximum value of the adhesive force when the probe is lifted is taken as the adhesive force peak, and the average value of the adhesive force peaks obtained by three measurements in total is taken as the viscosity value.

[0049] The elastic modulus of the filament for three-dimensional printing is preferably 10 to 700 MPa. If the elastic modulus of the filament for three-dimensional printing is within the above range, the three-dimensional shape achieved by three-dimensional printing is good. Furthermore, the storage property as a winding body is also excellent. The lower limit of the elastic modulus is preferably 15 MPa or more, more preferably 50 MPa or more, and further preferably 100 MPa or more. The upper limit of the elastic modulus is preferably 650 MPa or less, more preferably 600 MPa or less, and further preferably 550 MPa or less.

[0050] The total volume content of the continuous reinforcing fibers and the thermosetting resin in the filament for three-dimensional printing is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, further preferably 95% or more, particularly preferably 99% or more.

[0051] The thermosetting resin contained in the filament for three-dimensional printing is preferably in an uncured state. According to this method, the three-dimensional shape achieved by three-dimensional printing is good. It should be noted that in this specification, the uncured state of the thermosetting resin refers to the state before the curing of the thermosetting resin is completely completed, including not only a completely uncured state, but also a semi-cured state (partially cured state) to the extent that the curing (cross-linking) reaction is not completely completed.

[0052] Examples of the form of the filament for three-dimensional printing include fiber, tape, rope, and braid.

[0053] The shape of the cut surface in the direction orthogonal to the length direction of the filament for three-dimensional printing is preferably circular, flat or elliptical, more preferably flat or elliptical. If the cut surface is circular, flat or elliptical, the fiber breakage caused by the nozzle pressing pressure can be suppressed when ejected from the nozzle of the three-dimensional printer, and it is easy to manufacture a three-dimensional object with excellent mechanical properties and other properties. It should be noted that the shape of the cut surface in the direction orthogonal to the length direction of the filament for three-dimensional printing can also be a shape other than the above (for example, amorphous, square, etc.).

[0054] (Continuous reinforcement fiber)

[0055] The filament for three-dimensional printing of the present invention comprises continuous reinforcing fibers. In this specification, continuous reinforcing fibers refer to reinforcing fibers having an average fiber length of 30 mm or more, preferably reinforcing fibers having an average fiber length of 50 mm or more. There is no particular restriction on the average fiber length of the continuous reinforcing fibers, but from the viewpoint of forming processability, it is preferably 1 to 20,000 m, more preferably 100 to 10,000 m, and further preferably 1,000 to 7,000 m. The length of the fiber in the present invention is the weight average fiber length unless otherwise specified.

[0056] The volume content of the continuous reinforcing fibers in the filament for three-dimensional printing is preferably 10 to 80% by volume, more preferably 20 to 70% by volume, and further preferably 40 to 65% by volume. If the volume content of the continuous reinforcing fibers is within the above range, a molded product with excellent mechanical strength can be obtained. Furthermore, it is also possible to expect the improvement of printability and the improvement of the interlayer strength of the obtained three-dimensional shape.

[0057] In addition, the volume content rate of the continuous reinforcing fiber in the filament for three-dimensional printing refers to the value calculated by the following formula.

[0058] Volume content of continuous reinforcing fibers = (volume of continuous reinforcing fibers contained in 3D printing filament / volume of 3D printing filament) × 100

[0059] The number of single fibers of the continuous reinforcing fibers used in the filaments for three-dimensional printing is preferably more than 100, more preferably 100 to 60,000, and further preferably 100 to 24,000. That is, the continuous reinforcing fibers used in the filaments for three-dimensional printing are preferably fiber bundles formed by bundling more than 100 single fibers. If the number of single fibers of the continuous reinforcing fibers is more than 100, the fiber breakage caused by the nozzle pressing pressure can be suppressed when ejected from the nozzle of the three-dimensional printer, and it is easy to manufacture three-dimensional objects with excellent performance such as mechanical properties. In addition, if the number of single fibers of the continuous reinforcing fibers is 100 to 24,000, in addition to the above-mentioned effects, it can also be expected that effective fiber orientation can be implemented until the fine parts of the three-dimensional object. In addition, if the number of fibers is more than 6,000, it can also be expected that the effect of shortening the three-dimensional shaping time can be expected. In addition, the above-mentioned fiber bundle can be twisted. According to this method, the distortion of the fibers caused by the difference between the inner and outer diameters of the curved portion can be corrected for the trajectory of three-dimensional printing, making it easier to obtain a three-dimensional object with better mechanical properties and other characteristics.

[0060] The average fiber diameter of the above-mentioned single fiber is preferably 3 μm or more, more preferably 4 μm or more, and further preferably 5 μm or more. In addition, the average fiber diameter is preferably 50 μm or less, more preferably 20 μm or less, and further preferably 12 μm or less. It should be noted that the average fiber diameter of a single fiber refers to the average value of the diameter of the single fiber.

[0061] As the type of continuous reinforcing fiber, inorganic fibers such as glass fiber, carbon fiber, alumina fiber, boron fiber, ceramic fiber, metal fiber (steel fiber, etc.), and plant fiber (including kenaf (Kenaf), bamboo fiber, etc.), aramid fiber, polyoxymethylene fiber, aromatic polyamide fiber, polyphenylene benzobisoxazole fiber, organic fibers such as ultra-high molecular weight polyethylene fiber, etc. can be listed. Among them, it is preferably selected from at least one of carbon fiber, glass fiber and aramid fiber, and more preferably selected from at least one of carbon fiber and glass fiber. In particular, since it has excellent characteristics such as high strength and high elastic modulus although it is lightweight, it is preferred to use carbon fiber.

[0062] Examples of the carbon fiber include polyacrylonitrile (PAN)-based carbon fiber, petroleum / coal pitch-based carbon fiber, rayon-based carbon fiber, cellulose-based carbon fiber, lignin-based carbon fiber, phenolic carbon fiber, and vapor-grown carbon fiber.

[0063] The continuous reinforcing fibers can be treated with a treatment agent. As the treatment agent, sizing agents and surface treatment agents can be listed. For example, as the treatment agent, a treatment agent containing at least one selected from epoxy resins, polyurethane resins, silane coupling agents, water-insoluble polyamide resins and water-soluble polyamide resins can be listed. In addition, the treatment agent can also use the treatment agent described in paragraph numbers 0093 and 0094 of Japanese Patent No. 4894982, and the content is introduced into this specification. The amount of the treatment agent is preferably 0.001 to 1.5% by mass of the continuous reinforcing fibers, more preferably 0.1 to 1.2% by mass, and further preferably 0.5 to 1.1% by mass.

[0064] (Thermosetting resin composition)

[0065] The thermosetting resin composition used in the filament for three-dimensional printing of the present invention contains a thermosetting resin. The thermosetting resin composition is the matrix of the filament for three-dimensional printing. The content of the thermosetting resin in the thermosetting resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 80% by mass or more. In addition, the content of the thermosetting resin in the thermosetting resin composition may also be 90% by mass or more, 95% by mass or more, or 99% by mass or more. In addition, the thermosetting resin contained in the thermosetting resin composition is preferably a thermosetting resin that is solid at 25°C.

[0066] It should be noted that, in the present specification, being solid at 25° C. means that the viscosity at 25° C. is greater than 10000 mPa·s.

[0067] The melt viscosity of the thermosetting resin at any temperature of 40 to 250° C. is preferably 1 to 8500 mPa·s, more preferably 1 to 5000 mPa·s, and even more preferably 1 to 3000 mPa·s.

[0068] The weight average molecular weight of the thermosetting resin is preferably 200 to 50,000, more preferably 200 to 40,000, further preferably 200 to 30,000, and further preferably 200 to 25000. The softening point of the thermosetting resin is preferably 40 to 250°C, more preferably 70 to 250°C, and further preferably 80 to 250°C.

[0069] As the type of thermosetting resin, cyanate resin, bismaleimide triazine resin, phenolic resin, benzoxazine resin, unsaturated polyester resin, diallyl phthalate resin, maleimide resin, epoxy resin, vinyl ester resin, phenoxy resin, alkyd resin, polyurethane resin, carbamate acrylate resin, urea resin, melamine resin, etc. can be listed, wherein, preferably cyanate resin, bismaleimide triazine resin, phenolic resin, benzoxazine resin, epoxy resin and unsaturated polyester resin. Among them, from the viewpoint of generating less gas during curing reaction, thermosetting resin is preferably cyanate resin, bismaleimide triazine resin, benzoxazine resin and epoxy resin, more preferably cyanate resin and bismaleimide triazine resin. In addition, from the viewpoint of easy adjustment of curing speed and curing temperature range, thermosetting resin is preferably diallyl phthalate resin and unsaturated polyester resin.

[0070] The thermosetting resin may be used alone or in the form of a mixture of two or more thermosetting resins.

[0071] Examples of the cyanate resin include cyanate resins represented by formula (1).

[0072]

[0073] In formula (1), Ar1 represents a benzene ring, a naphthalene ring or a group formed by two benzene rings bonded by a single bond. When there are multiple groups, they may be the same or different. Ra each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a group formed by an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms. The aromatic ring in Ra may have a substituent, and the substituents in Ar1 and Ra may be selected at any position. p represents the number of cyano groups bonded to Ar1, and is independently an integer of 1 to 3. q represents the number of Ra bonded to Ar1, and when Ar1 is a benzene ring, q is 4-p, when Ar1 is a naphthalene ring, q is 6-p, and when Ar1 is a group formed by two benzene rings bonded by a single bond, q is 8-p. t represents the average number of repetitions, and is an integer of 0 to 50. The cyanate resin may be a mixture of compounds having different t. When there are multiple Zs, each independently represents a single bond, a divalent organic group having 1 to 50 carbon atoms (the hydrogen atom may be substituted by a heteroatom), a divalent organic group having 1 to 10 nitrogen atoms (for example, -NRN- (where R represents an organic group)), a carbonyl group (-CO-), a carboxyl group (-C(=O)O-), a carbonyl dioxide group (-OC(=O)O-), a sulfonyl group (-SO2-), a divalent sulfur atom or a divalent oxygen atom.

[0074] The alkyl group in Ra of formula (1) may have any one of a linear or branched chain structure and a cyclic structure (e.g., a cycloalkyl group, etc.). In addition, the hydrogen atoms in the alkyl group in formula (1) and the aryl group in Ra may be substituted by halogen atoms such as fluorine atoms, chlorine atoms, alkoxy groups such as methoxy groups, phenoxy groups, or cyano groups. As specific examples of alkyl groups, it is not limited to the following, and methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2,2-dimethylpropyl, cyclopentyl, hexyl, cyclohexyl, and trifluoromethyl groups may be listed. As specific examples of aryl groups, it is not limited to the following, and phenyl, xylene, 2,4,6-trimethylphenyl, naphthyl, phenoxyphenyl, ethylphenyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, dichlorophenyl, dicyanophenyl, trifluorophenyl, methoxyphenyl, and o-tolyl, m-tolyl or p-tolyl may be listed. Examples of the alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

[0075] Specific examples of the divalent organic group having 1 to 50 carbon atoms in Z of formula (1) include methylene, ethylene, trimethylene, cyclopentylene, cyclohexylene, trimethylcyclohexylene, biphenylmethylene, dimethylmethylene-phenylene-dimethylmethylene, fluorenediyl, and phthalidene. The hydrogen atoms in the divalent organic group may be substituted with halogen atoms such as fluorine atoms and chlorine atoms, alkoxy groups such as methoxy and phenoxy, and cyano groups.

[0076] Examples of the divalent organic group having 1 to 10 nitrogen atoms in Z of the formula (1) include an imino group and a polyimide group.

[0077] Examples of the organic group represented by Z in formula (1) include organic groups having structures represented by the following formula (2) or formula (3).

[0078]

[0079] In formula (2), Ar2 represents benzene tetrayl, naphthalene tetrayl or biphenyl tetrayl, and when u is 2 or more, they may be the same or different from each other. Rb, Rc, Rf, and Rg each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxyl group. Rd and Re each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. u represents an integer of 0 to 5.

[0080]

[0081] In formula (3), Ar3 represents benzene tetrayl, naphthalene tetrayl or biphenyl tetrayl, and when v is 2 or more, they may be the same or different. Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or an aryl group substituted with at least one cyano group. v represents an integer of 0 to 5.

[0082] Furthermore, as Z in formula (1), a divalent group represented by the following formula can be mentioned.

[0083] -O- -S-

[0084] In the above formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0085] Specific examples of Ar2 in formula (2) and Ar3 in formula (3) include 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene, 2,4'-biphenylene, 2,2'-biphenylene, 2,3'-biphenylene, 3,3'-biphenylene, 3,4'-biphenylene, 2,6-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,8-naphthylene, 1,3-naphthylene, 1,4-naphthylene and the like.

[0086] The alkyl group and aryl group in Rb, Rc, Rd, Re, Rf and Rg in the formula (2) and Ri and Rj in the formula (3) have the same meanings as the alkyl group and aryl group in Ra in the above formula (1).

[0087] Examples of the cyanate resin include phenol novolac type cyanate resin, biphenyl aralkyl type cyanate resin, bisphenol A type cyanate resin, diallyl bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol F type cyanate resin, bisphenol M type cyanate resin, naphthol aralkyl type cyanate resin, naphthylene ether type cyanate resin, xylene type cyanate resin, trisphenol methane type cyanate resin, and adamantane skeleton type cyanate resin. Preferred are naphthol aralkyl type cyanate resin, novolac type cyanate resin, and biphenyl aralkyl type cyanate resin, and more preferred are naphthol aralkyl type cyanate resin and novolac type cyanate resin.

[0088] The weight average molecular weight of the cyanate resin is preferably 200 to 25,000, more preferably 250 to 20,000, and further preferably 300 to 15,000.

[0089] Examples of the cyanate resin include CYTESTER (registered trademark) TA-1500 manufactured by Mitsubishi Gas Chemical Co., Ltd. and Primaset PT-15 and PT-30 manufactured by Lonza Japan Ltd.

[0090] As the bismaleimide triazine resin, there can be cited a bismaleimide triazine resin obtained by crosslinking a bismaleimide compound and a cyanate compound. As the bismaleimide compound, there can be cited bis(4-maleimide phenyl)methane, 2,2-bis{4-(4-maleimide phenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimide phenyl)methane, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, bis(3,5-diethyl-4-maleimide phenyl)methane, prepolymers of these maleimide compounds, etc. As the cyanate compound, there can be cited the above-mentioned cyanate resins, etc.

[0091] The weight average molecular weight of the bismaleimide triazine resin is preferably 200 to 25,000, more preferably 250 to 20,000, and even more preferably 300 to 15,000.

[0092] Examples of the bismaleimide triazine resin include BT-2160 and BT-2170 manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0093] As the diallyl phthalate resin, ISO DAP, DAP A, DAP S etc. manufactured by OSAKA SODA CO., LTD. are mentioned.

[0094] The thermosetting resin composition may further contain a curing agent component or a catalyst component (hereinafter also referred to as curing agents). The type of the curing agent can be appropriately selected according to the type of the thermosetting resin.

[0095] As curing agents when epoxy resin is used as a thermosetting resin, imidazole compounds and their derivatives; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine, etc. can be listed. They can be used alone or in combination of two or more. Among them, from the viewpoint of heat resistance, glass transition temperature and storage stability, imidazole compounds and their derivatives or phosphorus compounds can be used. As imidazole compounds, for example, methylimidazole, phenylimidazole, isocyanate-masked imidazole (for example, addition reaction products of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole, etc.) can be listed, preferably isocyanate-masked imidazole.

[0096] When using cyanate resin as a thermosetting resin, curing agents include imidazole compounds and their derivatives; carboxylates of manganese, cobalt, zinc, etc.; organic metal compounds such as acetylacetone complexes of transition metals such as manganese, cobalt, zinc, etc. These can be used alone or in combination of two or more. Among them, organic metal compounds are preferred from the viewpoints of heat resistance, glass transition temperature and storage stability.

[0097] When using bismaleimide triazine resin as a thermosetting resin, curing agents include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole, phenylimidazole, and isocyanate-masked imidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as diisopropyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane, tert-butyl peroxyisopropyl monocarbonate, and α,α'-bis(tert-butyl peroxide)diisopropylbenzene; carboxylates of manganese, cobalt, zinc, etc. These can be used alone or in combination of two or more. Among them, from the viewpoint of heat resistance, glass transition temperature and storage stability, imidazole compounds, organic peroxides and carboxylates are preferred. From the viewpoint of heat resistance, glass transition temperature, elastic modulus and thermal expansion coefficient, it is preferred to use imidazole compounds and organic peroxides in combination. In addition, among organic peroxides, α, α'-bis(tert-butyl peroxide) diisopropylbenzene is particularly preferred.

[0098] When using benzoxazine resin as a thermosetting resin, curing agents include imidazole curing accelerators, phosphorus curing accelerators, amine curing accelerators, etc. As imidazole curing accelerators, for example, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, etc. can be listed. As phosphorus curing accelerators, for example, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, etc. can be listed. As amine curing accelerators, for example, triethylamine, benzyldimethylamine, etc. can be listed. These can be used alone or in combination of two or more.

[0099] As curing agents when diallyl phthalate resin or unsaturated polyester resin is used as a thermosetting resin, organic peroxides can be cited. As organic peroxides, for example, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxybenzoate, tert-hexyl peroxy-2-ethylhexanoate, 1,1-di-tert-butyl peroxy-3,3,5-trimethylcyclohexane, etc. can be cited. These can be used alone or in combination of two or more.

[0100] When the thermosetting resin composition contains a curing agent, the content ratio of the curing agent is not particularly limited, and for example, it can be 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass relative to 100 parts by mass of the thermosetting resin A. If the curing agent is used within this range, better printability and storage stability can be obtained.

[0101] The thermosetting resin composition may contain a thermoplastic resin, a tackifier, an antioxidant, a stabilizer such as a heat stabilizer, a hydrolysis resistance improver, a weathering stabilizer, a matting agent, an ultraviolet absorber, a nucleating agent, a plasticizer, a dispersant, a flame retardant, an antistatic agent, a coloring inhibitor, a gelling inhibitor, a colorant, a mold release agent, etc., within a range that does not impair the desired properties. For details, reference may be made to the descriptions of Japanese Patent No. 4894982 and Japanese Patent No. 6645777, and the contents are incorporated into this specification.

[0102] <Rolled body>

[0103] The wound body of the present invention is formed by winding the above-mentioned 3D printing filament around a core material. The wound body of the present invention is mounted on a 3D printer, and the 3D printing filament is unwound from the wound body for use when manufacturing a three-dimensional object by 3D printing.

[0104] As the material of the core material, paper, resin, metal, etc. can be listed, without particular limitation. The diameter of the core material can be appropriately selected according to the type of the three-dimensional printer. For example, from the viewpoint of strength, it is preferably 100 mm or more, more preferably 200 mm or more, and further preferably 300 mm or more. The upper limit can be 1000 mm or less, or 1500 mm or less.

[0105] The winding length of the three-dimensional printing filament in the wound body varies depending on the shape and size of the three-dimensional printing filament, but is preferably 3 m or more, more preferably 5 m or more, and even more preferably 10 m or more.

[0106] <Method for producing filament for three-dimensional printing>

[0107] The filament for three-dimensional printing of the present invention can be produced by a step of impregnating continuous reinforcing fibers with a thermosetting resin composition containing a thermosetting resin. Examples of the continuous reinforcing fibers and the thermosetting resin composition include those mentioned above.

[0108] In the case of a thermosetting resin composition having properties that are not suitable for impregnation at room temperature, the thermosetting resin composition may be heated to increase fluidity to obtain a viscosity suitable for impregnation, or may be diluted with a solvent to obtain a viscosity suitable for impregnation and used as a resin solution.

[0109] As the solvent used in the manufacture of the resin solution, any solvent that dissolves the thermosetting resin is preferably used. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol and isopropanol, cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, and methyl hydroxyisobutyrate, polar solvents such as amides such as dimethylacetamide and dimethylformamide, and non-polar solvents such as aromatic hydrocarbons such as toluene and xylene. The boiling point of the solvent is preferably 30 to 160°C. If the boiling point of the solvent is within the above range, the solvent is easily removed in the drying process. The upper limit is preferably below 150°C, more preferably below 100°C, and further preferably below 80°C. The lower limit is preferably above 35°C, more preferably above 40°C, and further preferably above 50°C.

[0110] The content of the thermosetting resin in the resin solution is preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more.

[0111] The temperature of the resin solution is preferably 10 to 50°C, more preferably 10 to 40°C, further preferably 10 to 35°C, further preferably 15 to 30°C, further preferably 20 to 30°C, particularly preferably 20 to 25°C.

[0112] The viscosity of the resin solution at 25°C is preferably 1 to 2000 mPa·s. The lower limit may be 5 mPa·s or more, or 50 mPa·s or more. The upper limit may be 1500 mPa·s or less, or 1200 mPa·s or less, or 1000 mPa·s or less. As a preferred embodiment of the viscosity of the resin solution at 25°C, an embodiment of 5 to 1500 mPa·s can be listed. In addition, as another preferred embodiment of the viscosity of the resin solution at 25°C, an embodiment of 50 to 1200 mPa·s can be listed. In addition, as another preferred embodiment of the viscosity of the resin solution at 25°C, an embodiment of 1 to 1000 mPa·s can be listed.

[0113] Before the continuous reinforcing fibers are impregnated with the thermosetting resin composition, the continuous reinforcing fibers may be subjected to fiber opening treatment, preheating treatment, sizing treatment, etc. Such treatment can improve the impregnation property of the thermosetting resin composition.

[0114] The method for impregnating the continuous reinforcing fibers with the thermosetting resin composition is not particularly limited, and a known method may be adopted. For example, a method of impregnating the continuous reinforcing fibers with the thermosetting resin composition while stretching the continuous reinforcing fibers may be mentioned.

[0115] After the continuous reinforcing fibers are impregnated with the thermosetting resin composition, it is also preferred to heat in order to remove the solvent, remove the adhesiveness at room temperature caused by the promotion of the curing reaction of the thermosetting composition, or adjust the printability by promoting the curing reaction of the thermosetting composition. The heating temperature is not particularly limited, but is preferably 70 to 300°C, more preferably 90 to 250°C, and further preferably 100 to 200°C. The heating time is not particularly limited, but is preferably 1 to 270 seconds, more preferably 1 to 180 seconds, and further preferably 1 to 120 seconds from the perspective of productivity. In addition, when heating is performed, it is preferably performed under the condition that the thermosetting resin is not completely cured.

[0116] The three-dimensional printing filament of the present invention can be manufactured in this manner. Next, the three-dimensional printing filament manufactured in this manner is wound around a core material to manufacture the wound body of the present invention described above.

[0117] <Manufacturing method of molded product>

[0118] The method for manufacturing a molded product of the present invention is characterized in that the 3D printing filament of the present invention (hereinafter also simply referred to as filament) is ejected from a nozzle of a 3D printer onto a substrate to manufacture a three-dimensional object, and the three-dimensional object is heated.

[0119] As the three-dimensional printer, any three-dimensional printer using a molding method using a material extrusion deposition method is preferably used.

[0120] When manufacturing a three-dimensional object, it is also preferred to fix one end of the filament to the substrate and eject it from the nozzle. When ejecting the filament, the substrate may be moved to stack in a manner to form a desired shape, the nozzle may be moved to stack, or both the substrate and the nozzle may be moved to stack. From the viewpoint of improving productivity, it is preferred to move the nozzle to stack.

[0121] In addition, the distance between the front end of the nozzle and the base can be close (for example, less than 3 mm) or far (for example, more than 5 mm), but the closer the distance, the better the tracking of the filament. There is no special regulation on the ejection speed, for example, it can be 0.5 to 100 mm / second, 1 to 50 mm / second, 1 to 20 mm / second, or 1 to 10 mm / second. In addition, in the case of high speed, it can also be more than 20 mm / second and less than 100 mm / second.

[0122] When the filaments are ejected from the nozzle, it is preferred to heat the filaments before ejecting. The heating temperature of the filaments can be appropriately specified according to the type of thermosetting resin. It is preferably above the softening point of the thermosetting resin contained in the filaments and below the softening point + 150°C, and more preferably within the softening point + 120°C. In addition, the heating of the filaments is preferably performed in the nozzle.

[0123] In order to improve the printability, it is preferred to heat the substrate during the formation of the three-dimensional object. The heating temperature of the substrate is preferably 20 to 150°C, more preferably 20 to 130°C, and further preferably 20 to 100°C.

[0124] When manufacturing a three-dimensional object, a support material for supporting the space portion of the three-dimensional object can also be used.

[0125] When utilizing the method for manufacturing a molded article of the present invention, after manufacturing the above-mentioned three-dimensional object, the three-dimensional object is heated. By heating, the curing of the thermosetting resin is completed, and a molded article having excellent mechanical properties can be obtained. The heating temperature of the three-dimensional object can be appropriately specified according to the type of thermosetting resin. The heating temperature is preferably 50 to 400°C, more preferably 100 to 350°C. There is no limitation on the heating time, but it is preferably 10 to 36,000 seconds, more preferably 20 to 14,400 seconds, and further preferably 30 to 10,800 seconds.

[0126] The heating of the three-dimensional object can also be carried out by applying pressure. The pressure during the application of pressure can be appropriately specified according to the shape and size of the three-dimensional object. For example, it is preferably 1 kPa or more, more preferably 5 kPa or more, and further preferably 100 kPa or more. The upper limit is preferably 1000000 kPa or less, more preferably 500000 kPa or less, and further preferably 100000 kPa or less.

[0127] The molded product obtained in the present invention is widely used for fiber-reinforced resin molded products. There is no particular regulation on the field of use, and it is widely used in conveyor parts such as automobiles, general machinery parts, precision machinery parts, electronic and electrical equipment parts, OA equipment parts, building materials and housing-related parts, medical devices, leisure sports goods, game equipment, medical products, daily necessities such as food packaging films, defense and aerospace products, etc. It is also preferably used for their prototypes.

[0128] Example

[0129] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0130] (Example 1)

[0131] A resin solution was prepared by mixing 75 parts by mass of a cyanate resin (TA-1500 manufactured by Mitsubishi Gas Chemical Co., Ltd., a thermosetting resin that is solid at 25°C and has a weight average molecular weight of 3824), 0.05 parts by mass of a catalyst (zinc bisoctylate), and 25 parts by mass of methyl ethyl ketone. The viscosity of the resin solution at 25°C was 543 mPa·s.

[0132] Each fiber is extracted from a winding body of carbon fiber (6000 single fibers, average fiber diameter of 4-7 μm) having a length of more than 1 m, and mechanically applied tension while passing through multiple guide devices, thereby opening the fibers, and introducing them into a groove with a width of 80 mm and a length of 100 mm filled with the above-mentioned resin solution at 25°C, and extracted from the groove at a speed of 100 mm / min. The filaments extracted from the groove are clamped by two rubber rollers, and after squeezing out the excess resin, they are heated at 160°C for 20 seconds to produce filaments. The volume content of carbon fiber as a continuous reinforcing fiber of the filament is 55% by volume. In addition, the shape of the cut surface in the direction orthogonal to the length direction of the filament is flat. In addition, the thermosetting resin in the filament is in an uncured state.

[0133] (Example 2)

[0134] A resin solution was prepared by mixing 75 parts by mass of a naphthol aralkyl cyanate resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., a solid thermosetting resin at 25°C, with a weight average molecular weight of 600), 0.05 parts by mass of a catalyst (zinc dioctanoate), and 25 parts by mass of methyl ethyl ketone. The resin solution was used to prepare filaments in the same manner as in Example 1 except that the viscosity of the resin solution at 25°C was 450 mPa·s. The volume content of the carbon fiber as a continuous reinforcing fiber of the filament was 55 volume%. In addition, the shape of the cut surface in the direction orthogonal to the length direction of the filament was flat. In addition, the thermosetting resin in the filament was in an uncured state.

[0135] (Example 3)

[0136] A resin solution was prepared by mixing 75 parts by mass of bismaleimide triazine resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name BT-2170, a solid thermosetting resin at 25°C, and a weight average molecular weight of 2100), 0.05 parts by mass of a catalyst (zinc bisoctanoate), and 25 parts by mass of methyl ethyl ketone. The resin solution was used to prepare filaments in the same manner as in Example 1. The viscosity of the resin solution at 25°C was 550 mPa·s. The volume content of the carbon fiber as a continuous reinforcing fiber of the filament was 50% by volume. In addition, the shape of the cut surface in the direction orthogonal to the length direction of the filament was an ellipse. In addition, the thermosetting resin in the filament was in an uncured state.

[0137] (Example 4)

[0138] A resin solution was prepared by mixing 67 parts by mass of a phenolic resin (manufactured by Aica Kogyo Company, Limited, product name BRM-416T, a solid thermosetting resin at 25°C, weight average molecular weight 2880) and 33 parts by mass of methanol. The resin solution was used to prepare the filament in the same manner as in Example 1 except that the filament was prepared. The viscosity of the resin solution at 25°C was 476 mPa·s. The volume content of the carbon fiber as a continuous reinforcing fiber of the filament was 48% by volume. In addition, the shape of the cut surface in the direction orthogonal to the length direction of the filament was an ellipse. In addition, the thermosetting resin in the filament was in an uncured state.

[0139] (Example 5)

[0140] A resin solution was prepared by mixing 67 parts by mass of a benzoxazine resin (manufactured by Shikoku Chemical Industry Co., Ltd., product name Pd-type benzoxazine, a thermosetting resin that is solid at 25°C, and a weight-average molecular weight of 440) and 33 parts by mass of methyl ethyl ketone. The resin solution was used to prepare filaments in the same manner as in Example 1 except that the filaments were prepared. The viscosity of the resin solution at 25°C was 1203 mPa·s. The volume content of the carbon fiber as a continuous reinforcing fiber of the filaments was 48% by volume. In addition, the shape of the cross section in a direction orthogonal to the length direction of the filaments was an ellipse. In addition, the thermosetting resin in the filaments was in an uncured state.

[0141] (Example 6)

[0142] Bismaleimide triazine resin (Mitsubishi Gas Chemical Co., Ltd., product name BT-2160, semi-solid thermosetting resin at 25°C, weight average molecular weight 1200) was heated to 120°C for use, and the filament was manufactured in the same manner as in Example 1. The viscosity at 120°C was 100 mPa·s. The volume content of the carbon fiber as a continuous reinforcing fiber of the filament was 50 volume%. In addition, the shape of the cross section in the direction orthogonal to the length direction of the filament was an ellipse. In addition, the thermosetting resin in the filament was in an uncured state.

[0143] (Example 7)

[0144] Isobutyl alcohol-modified melamine resin (manufactured by Hitachi Chemical Co., Ltd., product name Melan 265, thermosetting resin in liquid form at 25°C, weight-average molecular weight 5130) was used as the resin solution. The viscosity at 25°C was 550 mPa·s. Each fiber was extracted from a winding body of carbon fibers having a length of more than 1 m (6,000 single fibers, and an average fiber diameter of 4 to 7 μm for a single fiber), and mechanical tension was applied while passing through multiple guide devices to open the fibers, and then introduced into a groove with a width of 80 mm and a length of 100 mm filled with the above-mentioned resin solution at 25°C, and extracted from the groove at a speed of 100 mm / min. The filaments extracted from the groove were clamped by two rubber rollers, and after squeezing out the excess resin, they were heated at 100°C for 20 seconds to produce filaments. In addition, the thermosetting resin in the filaments was in an uncured state.

[0145] (Example 8)

[0146] Isobutyl alcohol-modified melamine resin (manufactured by Hitachi Chemical Co., Ltd., product name Melan 265, thermosetting resin in liquid form at 25°C, weight average molecular weight 5130) was used as the resin solution. The viscosity at 25°C was 550 mPa·s. Each fiber was extracted from a winding body of carbon fibers having a length of more than 1 m (6,000 single fibers, average fiber diameter of 4 to 7 μm for single fibers), and mechanical tension was applied while passing through multiple guide devices to open the fibers, and then introduced into a groove with a width of 80 mm and a length of 100 mm filled with the above-mentioned resin solution at 25°C, and extracted from the groove at a speed of 100 mm / min. The filaments extracted from the groove were clamped by two rubber rollers, and after squeezing out the excess resin, they were heated at 250°C for 100 seconds to produce filaments.

[0147] (Example 9)

[0148] A resin solution was prepared by mixing 50 parts by mass of a cyanate resin (TA-1500 manufactured by Mitsubishi Gas Chemical Co., Ltd., a thermosetting resin that is solid at 25°C and has a weight average molecular weight of 3824), 0.05 parts by mass of a catalyst (zinc bisoctylate), and 50 parts by mass of methyl ethyl ketone. The viscosity of the resin solution at 25°C was 9 mPa·s.

[0149] Each fiber is extracted from a winding body of carbon fiber (6000 single fibers, average fiber diameter of 4-7 μm) having a length of more than 1 m, and mechanically applied tension while passing through multiple guides, thereby opening the fibers, and introducing them into a groove with a width of 144 mm and a length of 240 mm filled with the above-mentioned resin solution at 25°C, and extracted from the groove at a speed of 200 mm / min. The filaments extracted from the groove are heated at 180°C for 18 seconds to produce filaments. The volume content of carbon fiber as a continuous reinforcing fiber of the filament is 55 volume%. In addition, the shape of the cut surface in the direction orthogonal to the length direction of the filament is flat. In addition, the thermosetting resin in the filament is in an uncured state.

[0150] (Example 10)

[0151] A resin solution was prepared by mixing 50 parts by mass of a benzoxazine resin (manufactured by Shikoku Chemical Industry Co., Ltd., product name Pd-type benzoxazine, a thermosetting resin that is solid at 25°C, and a weight average molecular weight of 440) and 50 parts by mass of methyl ethyl ketone. The resin solution was used to prepare filaments in the same manner as in Example 1 except that the filaments were prepared. The viscosity of the resin solution at 25°C was 8 mPa·s. The volume content of the carbon fiber as a continuous reinforcing fiber of the filaments was 50% by volume. In addition, the shape of the cross section in a direction orthogonal to the length direction of the filaments was an ellipse. In addition, the thermosetting resin in the filaments was in an uncured state.

[0152] (Determination of viscosity)

[0153] The viscosity value of the filaments was measured by the following method.

[0154] (Test conditions)

[0155] Probe diameter: 10mm

[0156] Probe pressing load: 20kPa

[0157] Probe pressing time: 30 seconds

[0158] Probe pressing speed: 30mm / min

[0159] Probe lifting speed: 10mm / min

[0160] (step)

[0161] 1) The paralleled filaments are fixed on a sample stand adjusted to 23° C., 35° C., 100° C. or 150° C. If the size of the filaments is smaller than the probe diameter, multiple filaments are paralleled without gaps to a size of 10 mm×10 mm and fixed on the sample stand.

[0162] 2) The probe was pressed against the filament of the sample stage at a pressing speed of 30 mm / min, a load of 20 kPa was applied, and the pressing was performed for 30 seconds.

[0163] 3) The probe is lifted at a lifting speed of 10 mm / min.

[0164] 4) The maximum value of the adhesive force when the probe is lifted is taken as the adhesive force peak, and the average value of the adhesive force peaks obtained by three measurements in total is taken as the viscosity value.

[0165] [Table 1]

[0166]

[0167] In Example 7, since the viscosity value at 23° C. was high, the viscosity value at 35° C., the viscosity value at 100° C., and the viscosity value at 150° C. were not measured.

[0168] The filaments of Examples 1 to 10 are solid at 23°C. Among them, the filaments of Examples 1 to 6, 9, and 10 have low viscosity values ​​at 23°C and high viscosity values ​​at 100°C and 150°C. The filaments of Examples 1 to 6, 9, and 10, whose viscosity values ​​at 23°C are 0 to 3 kPa, are smoothly pulled out from the roll body compared to the filament of Example 7, whose viscosity value at 23°C exceeds 3 kPa. In addition, by using the filaments of Examples 1 to 6, 9, and 10 to produce three-dimensional shapes by three-dimensional printing, compared to the case where the filament of Example 7 is used to produce three-dimensional shapes by three-dimensional printing, the generation of contamination in a three-dimensional printer such as a creel can also be suppressed. In addition, the filaments of Examples 1 to 6, 9, and 10, whose viscosity values ​​at 100°C and 150°C are 3 kPa or more, are superior in three-dimensional shapeability by three-dimensional printing compared to the filament of Example 8, whose viscosity values ​​at 100°C and 150°C are less than 3 kPa.

[0169] [Manufacturing of molded products]

[0170] (Production Example 1)

[0171] The filaments of Examples 1 to 3, 6, and 9 are installed in a 3D printer (manufactured by Velleman), and a portion of the filaments is extracted and fixed to the substrate of the 3D printer. Next, at a spraying temperature (heating temperature inside the nozzle) of 190°C and a spraying speed of 15 mm / second, the filaments are sprayed onto the substrate in parallel with a spacing of 1.0 mm in the width direction, thereby forming a layered object with a width of 15 mm and a length of 100 mm. Furthermore, the filaments are sprayed in layers on the surface of the layered object with a spacing of 0.3 mm in the height direction to obtain a three-dimensional object. The filaments are repeatedly sprayed and stacked in a manner such that the thickness of the three-dimensional object becomes 2 mm. The obtained three-dimensional object has a thickness of 2 mm, a width of 15 mm, and a length of 100 mm. Next, the three-dimensional object is heated at 180°C for 30 minutes and at 250°C for 2 hours to manufacture a molded product.

[0172] (Production Example 2)

[0173] The filaments of Examples 4, 5, and 10 are installed in a 3D printer (manufactured by Velleman), and a portion of the filaments is extracted and fixed to the substrate of the 3D printer. Next, at a spraying temperature (heating temperature inside the nozzle) of 120°C and a spraying speed of 15 mm / sec, the filaments are sprayed onto the substrate in parallel with a spacing of 1.0 mm in the width direction, thereby forming a layered object with a width of 15 mm and a length of 100 mm. Furthermore, the filaments are sprayed in layers on the surface of the layered object with a spacing of 0.3 mm in the height direction to obtain a three-dimensional object. The filaments are repeatedly sprayed and stacked in a manner such that the thickness of the three-dimensional object becomes 2 mm. The obtained three-dimensional object has a thickness of 2 mm, a width of 15 mm, and a length of 100 mm. Next, the three-dimensional object is heated at 180°C for 30 minutes to manufacture a molded product.

Claims

1. A filament for three-dimensional printing, wherein a thermosetting resin composition containing a thermosetting resin is impregnated in continuous reinforcing fibers, and is solid at 25°C, has a viscosity of 0 to 3 kPa measured at 23°C and a probe pressing load of 20 kPa, and has a viscosity of 3 kPa or more measured at 100°C or 150°C and a probe pressing load of 20 kPa.

2. The filament for three-dimensional printing according to claim 1, wherein: The volume content of the continuous reinforcing fibers in the three-dimensional printing filament is 10 to 80 volume %.

3. The filament for three-dimensional printing according to claim 1 or 2, wherein: The number of single fibers of the continuous reinforcing fibers is 100 or more.

4. The filament for three-dimensional printing according to claim 1 or 2, wherein: The continuous reinforcing fiber is at least one selected from carbon fiber, glass fiber and aramid fiber.

5. The filament for three-dimensional printing according to claim 1 or 2, wherein: The weight average molecular weight of the thermosetting resin is 200 to 50,000.

6. The filament for three-dimensional printing according to claim 1 or 2, wherein: The softening point of the thermosetting resin is 40-250°C.

7. The filament for three-dimensional printing according to claim 1 or 2, wherein: The thermosetting resin is solid at 25°C.

8. The filament for three-dimensional printing according to claim 1 or 2, wherein: The thermosetting resin contains at least one selected from cyanate resin, bismaleimide triazine resin, phenolic resin, benzoxazine resin, epoxy resin, unsaturated polyester resin and diallyl phthalate resin.

9. The filament for three-dimensional printing according to claim 1 or 2, wherein: The shape of the cross section in a direction perpendicular to the longitudinal direction of the three-dimensional printing filament is circular, flat or elliptical. 10 . A wound body obtained by winding the three-dimensional printing filament according to claim 1 around a core material. 11 . A method for producing a filament for three-dimensional printing, which is the method for producing a filament for three-dimensional printing according to any one of claims 1 to 9, comprising the step of impregnating continuous reinforcing fibers with a thermosetting resin composition containing a thermosetting resin.

12. A method for manufacturing a molded product, wherein: A three-dimensional printing filament according to any one of claims 1 to 9 is ejected from a nozzle of a three-dimensional printer onto a substrate to produce a three-dimensional object, and the three-dimensional object is heated.

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