Three-dimensional fabrication material, fabricated article, and method for producing same

Abstract

Provided is a pellet-shaped three-dimensional fabrication material that contains the following resin (A) and the following resin (B), and contains 0.1-50 parts by mass of the resin (B) with respect to 100 parts by mass of the resin (A). Also provided is a method for producing a fabricated article, the method comprising a step for discharging the three-dimensional fabrication material from an extrusion nozzle. Resin (A): at least one of a polyvinyl chloride-based resin and a chlorinated polyvinyl chloride-based resin. Resin (B): a styrene-based copolymer resin having a Shore hardness of A90 or more.

Description

Materials for 3D printing, printed objects, and methods for manufacturing the same.

[0001] The present invention relates to a material for three-dimensional molding, a molded object, and a method for manufacturing the same, and more specifically, to a material for three-dimensional molding containing a polyvinyl chloride resin and / or a chlorinated polyvinyl chloride resin and a specific styrene copolymer resin, which exhibits excellent solidification characteristics during cooling after extrusion from an extrusion nozzle in three-dimensional molding (hereinafter sometimes referred to as "3D molding"), a molded object using this three-dimensional molding material, and a method for manufacturing this molded object.

[0002] In recent years, 3D printers (hereinafter sometimes referred to as "3D printers") using various additive manufacturing methods (e.g., binder injection, material extrusion, powder bed fusion, and liquid bath photopolymerization) have been sold. Among these, in the material extrusion method, the molding material is inserted into the extrusion head as a filament or pellet made of thermoplastic resin, and is continuously extruded from the nozzle part of the extrusion head onto an X-Y planar substrate in the chamber while being heated and melted. The extruded resin is deposited and fused onto an already deposited resin laminate, and as it cools, it solidifies as a single unit. Because the material extrusion method is such a simple system, it has come to be widely used. Among these three-dimensional fabrication methods, those that use filament-shaped 3D fabrication materials are generally called Fused Filament Fabrication (FFF), while those that use pellet-shaped 3D fabrication materials are generally called Fused Granular Fabrication (FGF).

[0003] Conventionally, polyvinyl chloride resin (PVC) has been proposed as a thermoplastic resin used in 3D printing materials by material extrusion. For example, Patent Document 1 describes a thermoplastic polymer using PVC for 3D printing by filament extrusion. Patent Document 1 also describes that PVC can be blended with other thermoplastic resins such as ABS. Patent Document 2 describes that a blend of resins such as PVC and ABS can be used as a thermoplastic resin for 3D printing filaments.

[0004] As mentioned above, in material extrusion methods, materials such as filaments and pellets are usually used as molding materials. However, if the filament is too hard it will break, and if it is too soft it will collapse and cannot be transported, so there are many limitations on the materials that can be used.

[0005] In contrast, FGF 3D printing, which uses pellet-shaped 3D printing materials, has the following advantages over FFF 3D printing, which uses filament-shaped 3D printing materials: (1) It is not subject to the same limitations as filaments and can handle a wide range of materials. (2) Various additives such as pigments can be easily mixed in at the same time as printing, and it is also suitable for the use of recycled materials. (3) There is no need to process the resin pellets into a filament shape, and ordinary resin pellets such as injection molding materials can be used as is. (4) It is possible to print with a large extrusion width using a 3D printer with a large nozzle diameter, resulting in high printing efficiency and the ability to easily print large objects. For these reasons, FGF 3D printing, which uses pellet-shaped 3D printing materials, has been attracting attention in recent years.

[0006] Special table 2018-533669 Publication Special table 2024-500045

[0007] In 3D printing, when the molten resin extruded from the nozzle cools and solidifies, it is important that the solidification rate is appropriately fast and that it solidifies appropriately early (hereinafter, in this invention, this characteristic will be referred to as "solidification characteristics during cooling after extrusion from the nozzle" or simply "solidification characteristics during cooling") for the appearance, accuracy, efficiency, and yield of the resulting molded object. In particular, in FGF 3D printing, compared to FFF 3D printing, a 3D printer with a larger nozzle diameter is used and a larger extrusion width is used for printing, so the extruded molten resin is more difficult to cool. The inventors' investigations revealed that PVC, in particular, has poor solidification characteristics during cooling, and therefore it is necessary to improve these solidification characteristics during cooling.

[0008] However, previous technologies had not proposed any techniques to solve the problems of solidification characteristics during cooling of PVC in 3D printing, particularly in FGF 3D printing. As mentioned above, Patent Documents 1 and 2 describe the possibility of blending ABS with PVC, but no specific studies have been conducted on combining PVC and ABS, etc. Moreover, Patent Documents 1 and 2 concern FFF 3D printing and do not consider solidification characteristics during cooling in 3D printing, particularly in FGF 3D printing.

[0009] The present invention aims to solve the problems of the above-mentioned prior art and to provide a pellet-shaped 3D printing material and a printed object made using this 3D printing material, which have excellent solidification characteristics during cooling after extrusion from a nozzle in FGF 3D printing of PVC resins and are useful for improving the appearance, printing accuracy, printing efficiency, and printing yield of the resulting printed object.

[0010] The inventors of this invention conducted extensive research to solve the above problems and, as a result, discovered that the above problems can be solved by a three-dimensional molding material obtained by blending a specific styrene copolymer resin with a polyvinyl chloride resin and / or chlorinated polyvinyl chloride resin in a predetermined ratio, leading to the development of the present invention.

[0011] In other words, the gist of this invention is as follows:

[0012] [1] A pellet-shaped three-dimensional molding material comprising the following resin (A) and the following resin (B), wherein the amount of resin (B) is 0.1 parts by mass or more, 1 part by mass or more, 5 parts by mass or more, 7 parts by mass or more, 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less per 100 parts by mass of resin (A). Resin (A): At least one resin of polyvinyl chloride resin and chlorinated polyvinyl chloride resin Resin (B): Styrene copolymer resin having a Shore hardness of A90 or higher, D40 or higher, or D60 or higher

[0013] [2] The three-dimensional molding material according to [1], wherein the average degree of polymerization of the resin (A) is 3800 or less, 3500 or less, 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 700 or less, or 500 or less. [3] The three-dimensional molding material according to [1] or [2], wherein the resin (B) is at least one selected from the group consisting of acrylonitrile-butadiene-styrene resin, acrylonitrile-ethylenepropylene-styrene resin, acrylonitrile-styrene resin, methyl methacrylate-butadiene-styrene resin, butadiene-styrene resin, and acrylate-styrene-acrylonitrile resin. [4] The three-dimensional molding material according to any one of [1] to [3], wherein the total content ratio of the resin (A) and the resin (B) is 50% by mass or more, 60% by mass or more, or 70% by mass or more. [5] The three-dimensional molding material according to any one of [1] to [4], wherein the average degree of polymerization of the resin (A) is 300 or more or 400 or more.

[0014] [6] A three-dimensional molding material according to any one of [1] to [5], wherein the total content ratio of resin (A) and resin (B) is 100% by mass, 100% by mass or less, or 95% by mass or less. [7] A three-dimensional molding material according to any one of [1] to [6], wherein the mass ratio of the blended amounts of resin (A) and resin (B) [resin (B)] / [resin (A)] is 0.01 or more or 0.03 or more. [8] A three-dimensional molding material according to any one of [1] to [7], wherein the mass ratio of the blended amounts of resin (A) and resin (B) [resin (B)] / [resin (A)] is 0.3 or less or 0.2 or less.

[0015] [9] The three-dimensional molding material according to any one of [1] to [8], wherein the resin (B) contains 50% by mass or more, 55% by mass or more, or 60% by mass or more of aromatic vinyl monomer units.

[10] The three-dimensional molding material according to any one of [1] to [9], wherein the resin (B) contains 90% by mass or less, 80% by mass or less, or 75% by mass or less of aromatic vinyl monomer units.

[11] The three-dimensional molding material according to any one of [1] to

[10] , wherein the resin (B) contains 10% by mass or more, 20% by mass or more, or 25% by mass or more of one or more of vinyl cyanide monomer units, rubbery polymer units, and other monomer units.

[12] The resin (B) comprises 50% by mass or less, 45% by mass or less, or 40% by mass or less one or more of vinyl cyanide monomer units, rubbery polymer units, and other monomer units, respectively, as a three-dimensional molding material according to any one of [1] to

[11] .

[0016]

[13] The melt volume rate of the resin (B), measured in accordance with ISO 1133 at 220°C and 10 kgf, is 1 cm ３ / 10 minutes or more or 2 cm ３ A three-dimensional molding material according to any one of [1] to

[12] , wherein the melt volume rate of the resin (B), measured in accordance with ISO 1133 at 220°C and 10 kgf, is 100 cm². ３ / 10 minutes or less or 50 cm ３ A three-dimensional molding material according to any one of [1] to

[13] , wherein the melt mass flow rate measured at 200°C and a load of 2.16 kg in accordance with JIS 7210 (ISO 1133) is 1 g / 10 min or more or 2 g / 10 min or more.

[16] A three-dimensional molding material according to any one of [1] to

[15] , wherein the melt mass flow rate measured at 200°C and a load of 2.16 kg in accordance with JIS 7210 (ISO 1133) is 50 g / 10 min or less or 30 g / 10 min or less.

[0017]

[17] A molded object made by molding a three-dimensional material according to any one of [1] to

[16] using a three-dimensional printer, wherein the extrusion width during molding is 1 mm or more, 1.5 mm or more, or 2 mm or more.

[18] The molded object according to

[17] , wherein the extrusion width during molding is 20 mm or less or 15 mm or less.

[19] A molded object made by molding a three-dimensional material according to any one of [1] to

[16] using a three-dimensional printer, wherein the extrusion width during molding is 20 mm or less or 15 mm or less.

[0018]

[20] A method for manufacturing a molded object, comprising the step of extruding a three-dimensional molding material described in any of [1] to

[16] from an extrusion nozzle.

[21] The method for manufacturing a molded object according to

[20] , wherein in the step of extruding the three-dimensional molding material from an extrusion nozzle, the temperature of the molten resin extruded from the extrusion nozzle is 120°C or higher, 150°C or higher, 220°C or lower, or 200°C or lower.

[22] The method for manufacturing a molded object according to

[20] or

[21] , wherein in the step of extruding the three-dimensional molding material from an extrusion nozzle, the diameter of the extrusion nozzle is 0.5 mm or higher, 1 mm or higher, 1.5 mm or higher, or 2 mm or higher.

[23] The method for manufacturing a molded object according to any of

[20] to

[22] , wherein in the step of extruding the three-dimensional molding material from an extrusion nozzle, the diameter of the extrusion nozzle is 20 mm or less, 15 mm or less, or 10 mm or less.

[24] A method for manufacturing a molded object according to any one of

[20] to

[23] , wherein the step of extruding the three-dimensional molding material from an extrusion nozzle is a step of using a three-dimensional printer equipped with a raw material supply unit, a melting extrusion unit for supplied raw materials, and an extrusion nozzle for extruding molten resin, in which the three-dimensional molding material introduced from the raw material supply unit is fed to the extrusion nozzle while being melted and extruded from the extrusion nozzle.

[0019]

[25] Use for three-dimensional molding of a pellet-shaped material comprising the following resin (A) and the following resin (B), wherein the amount of resin (B) is 0.1 parts by mass or more, 1 part by mass or more, 5 parts by mass or more, 7 parts by mass or more, 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less per 100 parts by mass of resin (A). Resin (A): At least one resin of polyvinyl chloride resin and chlorinated polyvinyl chloride resin Resin (B): Styrene copolymer resin having a Shore hardness of A90 or higher, D40 or higher, or D60 or higher

[0020]

[26] Use in three-dimensional molding in

[25] , wherein the average degree of polymerization of resin (A) is 3800 or less, 3500 or less, 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 700 or less, or 500 or less.

[27] Use in three-dimensional molding in

[25] or

[26] , wherein resin (B) is at least one selected from the group consisting of acrylonitrile-butadiene-styrene resin, acrylonitrile-ethylenepropylene-styrene resin, acrylonitrile-styrene resin, methyl methacrylate-butadiene-styrene resin, butadiene-styrene resin, and acrylate-styrene-acrylonitrile resin.

[28] Use in three-dimensional molding in any of

[25] to

[27] , wherein the total content ratio of resin (A) and resin (B) is 50% by mass or more, 60% by mass or more, or 70% by mass or more.

[29] In any of

[25] to

[28] , the average degree of polymerization of the resin (A) is 300 or more or 400 or more, for use in three-dimensional molding.

[0021]

[30] Use in three-dimensional molding in any of

[25] to

[29] , where the total content ratio of resin (A) and resin (B) is 100% by mass, 100% by mass or less, or 95% by mass or less.

[31] Use in three-dimensional molding in any of

[25] to

[30] , where the mass ratio of the blended amounts of resin (A) and resin (B) [resin (B)] / [resin (A)] is 0.01 or more or 0.03 or more.

[32] Use in three-dimensional molding in any of

[25] to

[31] , where the mass ratio of the blended amounts of resin (A) and resin (B) [resin (B)] / [resin (A)] is 0.3 or less or 0.2 or less.

[0022]

[33] In any of

[25] to

[32] , the resin (B) contains 50% by mass or more, 55% by mass or more, or 60% by mass or more of aromatic vinyl monomer units for use in three-dimensional molding.

[34] In any of

[25] to

[33] , the resin (B) contains 90% by mass or less, 80% by mass or less, or 75% by mass or less of aromatic vinyl monomer units for use in three-dimensional molding.

[35] In any of

[25] to

[34] , the resin (B) contains 10% by mass or more, 20% by mass or more, or 25% by mass or more of one or more of vinyl cyanide monomer units, rubbery polymer units, and other monomer units for use in three-dimensional molding.

[36] In any of

[25] to

[35] , the resin (B) contains 50% by mass or less, 45% by mass or less, or 40% by mass or less one or more of vinyl cyanide monomer units, rubber polymer units, and other monomer units, for use in three-dimensional molding.

[0023]

[37] In any of

[25] to

[36] , the melt volume rate of the resin (B), measured in accordance with ISO 1133 at 220°C and 10 kgf, is 1 cm ３ / 10 minutes or more or 2 cm ３ / For use in 3D modeling, which is 10 minutes or more.

[38] In any of

[25] to

[37] , the melt volume rate of the resin (B), measured in accordance with ISO 1133 at 220°C and 10 kgf, is 100 cm ３ / 10 minutes or less or 50 cm ３ Use for 3D modeling, where the melt mass flow rate of the 3D modeling material measured at 200°C and a load of 2.16 kg in accordance with JIS 7210 (ISO 1133) is 1 g / 10 min or more or 2 g / 10 min or more.

[39] Use for 3D modeling, where the melt mass flow rate of the 3D modeling material measured at 200°C and a load of 2.16 kg in accordance with JIS 7210 (ISO 1133) is 50 g / 10 min or less or 30 g / 10 min or less.

[0024] The 3D printing material of the present invention exhibits excellent solidification characteristics during cooling after extrusion from the nozzle in FGF3D printing. Therefore, using the 3D printing material of the present invention, it is possible to efficiently manufacture objects with a good appearance, excellent printing accuracy, and high printing yield. The objects produced by the present invention are 3D printed using this 3D printing material with an extrusion width of 1 mm or more, exhibiting excellent appearance, productivity, and other characteristics, and can be widely applied to various applications.

[0025] (a) Figure is a schematic diagram illustrating the main parts of a 3D printer, showing an example of an embodiment of the manufacturing method for molded objects according to the present invention. (b) Figure is an enlarged view of a cross-section along the line II-II in Figure (a).

[0026] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). This embodiment is illustrative for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented in various modifications within the scope of its gist.

[0027] [Material for 3D Modeling] The material for 3D modeling of the present invention is a pellet-shaped material for 3D modeling that contains the following resin (A) and the following resin (B), with the amount of resin (B) being 0.1 to 50 parts by mass per 100 parts by mass of resin (A). Resin (A): At least one resin from polyvinyl chloride resin and chlorinated polyvinyl chloride resin Resin (B): Styrene copolymer resin having a Shore hardness of A90 or higher

[0028] [Mechanism] The details of the mechanism by which the 3D modeling material of the present invention, by containing the above-mentioned resin (A) and resin (B), obtains the effect of excellent solidification characteristics during cooling after extrusion from the nozzle in FGF3D modeling are not clear. However, it is thought that by adding resin (B), which is an amorphous resin that has good miscibility and compatibility with resin (A) and has a higher glass transition temperature than resin (A), the glass transition temperature of the 3D modeling material can be shifted to the higher temperature side, making it easier to solidify during cooling after melting. Here, the resin (B) mixed with resin (A) needs to be a hard resin (not an elastomer) with a hardness at room temperature of a predetermined value or higher, from the viewpoint of solidifying after melting and giving the modeled object a certain hardness. For this reason, in the present invention, resin (B) with a Shore hardness of a specific value or higher is used.

[0029] [Resin (A)] The three-dimensional molding material of the present invention includes a polyvinyl chloride resin and / or a chlorinated polyvinyl chloride resin as resin (A). The chlorinated polyvinyl chloride resin is obtained by increasing the chlorine content of a polyvinyl chloride resin through chlorination treatment. The chlorine content of the polyvinyl chloride resin is usually less than 65% by mass, and more preferably 60% by mass or less. The chlorine content of the chlorinated polyvinyl chloride resin is usually 55% by mass or more, and more preferably 60% by mass or more. When the chlorine content of the polyvinyl chloride resin or chlorinated polyvinyl chloride resin is below the upper limit, it is superior in terms of processability and moldability, and when it is above the lower limit, it is superior in terms of heat deformation resistance and flame retardancy.

[0030] In the present invention, one type of polyvinyl chloride resin may be used as resin (A), or two or more types may be used. Alternatively, one type of chlorinated polyvinyl chloride resin may be used, or two or more types may be used. Furthermore, one or more types of polyvinyl chloride resins may be used in combination with one or more types of chlorinated polyvinyl chloride resins.

[0031] <Polyvinyl Chloride Resins> Polyvinyl chloride resins (hereinafter sometimes abbreviated as "PVC") may be polymers or copolymers produced by conventional methods such as suspension polymerization, bulk polymerization, microsuspension polymerization, or emulsion polymerization, using vinyl chloride or a mixture of vinyl chloride and monomers copolymerizable therein. Polyvinyl chloride resins may also be polyvinyl chloride resins that contain crosslinked gel components insoluble in tetrahydrofuran (hereinafter referred to as "THF"), which have been crosslinked by adding a crosslinking agent during polymerization.

[0032] Examples of monomers copolymerizable with vinyl chloride include, but are not limited to, vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate; acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; maleic acid esters such as dibutyl maleate and diethyl maleate; fumaric acid esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether, and vinyl octyl ether; vinyl cyanides such as acrylonitrile and methacrylonitrile; α-olefins such as ethylene, propylene, and styrene; vinylidene halides or vinyl halides other than vinyl chloride, such as vinylidene chloride and vinyl bromide; and polyfunctional monomers such as diallyl phthalate and ethylene glycol dimethacrylate. These monomers may be used individually or in combination of two or more.

[0033] When the polyvinyl chloride resin is a copolymer of vinyl chloride and other monomers, the content of constituent units derived from other monomers in the polyvinyl chloride resin is preferably 30% by mass or less, and more preferably 20% by mass or less, from the viewpoint of compatibility with the polyvinyl chloride resin.

[0034] The average degree of polymerization of the polyvinyl chloride resin is preferably 3800 or less, more preferably 3500 or less, more preferably 3000 or less, even more preferably 2500 or less, particularly preferably 2000 or less, especially preferably 1500 or less, extremely preferably 700 or less, and most preferably 500 or less, from the viewpoint of imparting good fluidity, based on JIS K6721. When the average degree of polymerization of the polyvinyl chloride resin is below the above upper limit, it is easier to obtain appropriate fluidity (MFR) during melting of the 3D molding material without adding a large amount of plasticizer, thus eliminating the need for excessive plasticizer addition and making it easier to prevent deterioration of solidification characteristics during cooling, which is preferable. The lower limit of the average degree of polymerization of the polyvinyl chloride resin is preferably 300 or more, and more preferably 400 or more, from the viewpoint of mechanical strength and impact resistance.

[0035] In the present invention, a cross-linked polyvinyl chloride resin containing the aforementioned cross-linked gel component can be used as the polyvinyl chloride resin for the purpose of controlling the design surface of the resulting molded object. When the cross-linked polyvinyl chloride resin contains a cross-linked gel component that is insoluble in THF, it is desirable that the content of the cross-linked gel component in the cross-linked polyvinyl chloride resin is usually 60% by mass or less, preferably 50% by mass or less, and that the average degree of polymerization of the portion dissolved in THF is within the above range. The cross-linked polyvinyl chloride resin may be used as is with the aforementioned cross-linked gel component, or a resin with a gel component exceeding the above amount may be manufactured and used after adjusting the content of the cross-linked gel component by appropriately blending it with an uncross-linked polyvinyl chloride resin. When the cross-linked gel component is below the above upper limit, it is preferable from the viewpoint of mechanical properties such as the tensile strength of the resulting molded object.

[0036] In this invention, the THF-insoluble crosslinked gel component is defined as the percentage of the weight of the insoluble component obtained after adding 2 g of polyvinyl chloride resin to 30 mL of THF while stirring, leaving it at 25°C for 24 hours, filtering it using Teflon® filter paper (mesh size 1 μm), and repeating this operation three times.

[0037] Incidentally, when an uncrosslinked polyvinyl chloride resin is used as the polyvinyl chloride resin, a shaped article with a glossy appearance can be obtained. Also, when a crosslinked polyvinyl chloride resin is used as the polyvinyl chloride resin, a shaped article with a non-glossy appearance can be obtained. These can be appropriately selected and used according to the application for which the shaped article of the present invention is applied.

[0038] The polyvinyl chloride resin may be used alone, or two or more different ones such as those having different copolymer compositions, average polymerization degrees, presence or absence of crosslinking, etc. may be used in combination.

[0039] <Chlorinated polyvinyl chloride resin> As described above, the chlorinated polyvinyl chloride resin is obtained by subjecting the polyvinyl chloride resin as described above, preferably the polyvinyl chloride resin having the above average polymerization degree, to chlorination treatment to increase the chlorine content (also referred to as "chlorination degree").

[0040] The chlorination method may be either gas phase or liquid phase. The chlorine content of the chlorinated polyvinyl chloride resin is preferably 50 to 80% by mass, more preferably 60 to 70% by mass, from the viewpoints of heat resistance to deformation and improvement of flame retardancy.

[0041] Regarding the chlorinated polyvinyl chloride resin, only one kind may be used, or two or more different polyvinyl chloride resins before chlorination or those having different chlorination degrees may be used in combination.

[0042] [Resin (B)] The three-dimensional shaping material of the present invention contains a styrene copolymer resin having a Shore hardness of A90 or more as resin (B). In the present invention, the styrene copolymer resin is a resin obtained by copolymerizing an aromatic vinyl monomer and one or more selected from other vinyl monomers copolymerizable with the aromatic vinyl monomer and a rubbery polymer. The styrene copolymer resin is usually a resin having a content of aromatic vinyl monomer units of 50% by mass or more.

[0043] Aromatic vinyl monomers used in styrene copolymer resins include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromstyrene, dibromstyrene, fluorostyrene, tribromstyrene, and other styrene derivatives, with styrene being particularly preferred. These may be used individually or in combination of two or more.

[0044] Other vinyl monomers copolymerizable with these aromatic vinyl monomers are preferably vinyl cyanide monomers, such as acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.

[0045] Furthermore, other monomers besides vinyl cyanide monomers that can copolymerize with aromatic vinyl monomers include: aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, and dodecyl acrylate; aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate; methyl methacrylate, etc. Examples include alkyl esters of methacrylic acid such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, and dodecyl methacrylate; epoxy group-containing methacrylic acid esters such as glycidyl methacrylate; maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide; and α,β-unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid. Preferably, alkyl acrylates and alkyl methacrylates are used. These other monomers may be used individually or in combination of two or more.

[0046] Furthermore, as a rubbery polymer copolymerizable with aromatic vinyl monomers, rubber with a glass transition temperature of 10°C or lower is preferred. Specific examples of such rubbery polymers include diene rubber, acrylic rubber, ethylene-propylene rubber, silicone rubber, and composite rubber (IPN-type rubber) having a structure in which the polyorganosiloxane rubber component and the polyalkyl (meth)acrylate rubber component are intertwined in such a way that they cannot be separated. Diene rubber and acrylic rubber are preferred. In this specification, "(meth)acrylate" refers to either or both "acrylate" and "methacrylate," and the same applies to "(meth)acrylic" and "(meth)acrylo."

[0047] Examples of diene-based rubbers include polybutadiene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene copolymers, polyisoprene, butadiene-isoprene copolymers, copolymers of ethylene, propylene, and non-conjugated dienes such as ethylene-propylene-hexadiene copolymers, butadiene-(meth)acrylic acid lower alkyl ester copolymers, and butadiene-styrene-(meth)acrylic acid lower alkyl ester copolymers. Examples of the above-mentioned (meth)acrylic acid lower alkyl esters include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. The proportion of the (meth)acrylic acid lower alkyl ester in the butadiene-(meth)acrylic acid lower alkyl ester copolymer or butadiene-styrene-(meth)acrylic acid lower alkyl ester copolymer is preferably 30% by mass or less of the amount of the rubbery polymer.

[0048] Examples of acrylic rubbers include alkyl acrylate rubber, where the alkyl group preferably has 1 to 8 carbon atoms. Specific examples of alkyl acrylates include ethyl acrylate, butyl acrylate, and hexyl acrylate. Optionally, ethylenically unsaturated monomers may be used in the alkyl acrylate rubber. Specific examples of such compounds include di(meth)acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth)acrylate, butadiene, and isoprene. Further examples of acrylic rubbers include core-shell polymers having a crosslinked diene rubber as the core.

[0049] These rubbery polymers may be used individually or in combination of two or more types.

[0050] The styrene copolymer resin preferably consists of 50 to 90% by mass of the above-mentioned aromatic vinyl monomer units and 10 to 50% by mass of one or more of the following: vinyl cyanide monomer units, rubbery polymer units, and other monomer units; more preferably consists of 55 to 80% by mass of aromatic vinyl monomer units and 20 to 45% by mass of one or more of the following: vinyl cyanide monomer units, rubbery polymer units, and other monomer units; and even more preferably consists of 60 to 75% by mass of aromatic vinyl monomer units and 25 to 40% by mass of one or more of the following: vinyl cyanide monomer units, rubbery polymer units, and other monomer units. The upper and lower limits of these values ​​can be combined as appropriate.

[0051] From the viewpoint of excellent compatibility with PVC, preferred styrene copolymer resins for the present invention include acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene resin (SAN), acrylonitrile-ethylenepropylene-styrene resin (AES), methyl methacrylate-butadiene-styrene resin (MBS), butadiene-styrene resin (BS), and acrylate-styrene-acrylonitrile (ASA) resin. Of these, ABS is particularly preferred because it exhibits excellent impact resistance and interlayer adhesion of the resulting molded products.

[0052] The styrene copolymer resin used as resin (B) has a Shore hardness of A90 or more. When the Shore hardness of the styrene copolymer resin as resin (B) is A90 or more, the effect of improving the solidification characteristics during cooling in the present invention can be sufficiently obtained. From the viewpoint of the solidification characteristics during cooling, the Shore hardness of the styrene copolymer resin of resin (B) is preferably D40 or more, more preferably D60 or more. There is no particular limitation on the upper limit of the Shore hardness of the styrene copolymer resin of resin (B), but the Shore hardness obtained in terms of composition is usually D90 or less.

[0053] In the present invention, the Shore hardness is a value measured 15 seconds after pressing the indenter of the durometer against a 6 mm thick sample using a type A or type D durometer in accordance with JIS K 6253. When the value shown by the type A durometer is 90 or more, it is measured with a type D durometer and the value is taken as the Shore hardness.

[0054] Further, the styrene copolymer resin used as resin (B) has an MVR (melt volume rate) of 1 to 100 cm ３ / 10 min, particularly preferably 2 to 50 cm ３ / 10 min. If the MVR of the styrene copolymer resin of resin (B) is at least the above lower limit, the fluidity of the three-dimensional shaping material is good, the discharge during shaping is stable, and the appearance of the shaped object is excellent. If it is at most the above upper limit, dripping of the resin from the nozzle during shaping can be suppressed by not reducing the viscosity of the three-dimensional shaping material too much.

[0055] Here, the MVR (melt volume rate) of the styrene copolymer resin is a value measured under the conditions of 220°C and 10 kgf in accordance with ISO 1133 using a melt indexer.

[0056] In the present invention, only one kind of styrene copolymer resin as resin (B) may be used, or two or more kinds having different copolymer component compositions, physical properties such as Shore A hardness, MVR, etc. may be mixed and used.

[0057] [Content ratio of resin (A) and resin (B)] The three-dimensional molding material of the present invention contains 0.1 to 50 parts by mass of resin (B) per 100 parts by mass of resin (A). When the content of resin (B) is 0.1 parts by mass or more per 100 parts by mass of resin (A), the effect of improving the solidification characteristics during cooling of the present invention, as described above, can be sufficiently obtained by using resin (B) in combination with resin (A). On the other hand, when the content ratio of resin (B) exceeds 50 parts by mass per 100 parts by mass of resin (A), the flame retardant performance of resin (A) is not easily exhibited. From this viewpoint, the content ratio of resin (B) per 100 parts by mass of resin (A) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more. On the other hand, the content ratio of resin (B) per 100 parts by mass of resin (A) is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

[0058] Furthermore, from the viewpoint of more effectively obtaining the effects of the present invention by containing resin (A) and resin (B) in the three-dimensional molding material of the present invention, the total content ratio of resin (A) and resin (B) in the three-dimensional molding material (100% by mass) of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. There is no particular upper limit to the total content ratio of resin (A) and resin (B), and it may be 100% by mass, but from the viewpoint of ensuring the content ratio of other components described later, it is usually 95% by mass or less.

[0059] The mass ratio of the blended amounts of resin (A) to resin (B), [resin (B)] / [resin (A)], is preferably 0.01 or higher, and more preferably 0.03 or higher. Furthermore, the mass ratio of the blended amounts of resin (A) to resin (B), [resin (B)] / [resin (A)], is preferably 0.3 or lower, and more preferably 0.2 or lower. If the blended mass ratio of resin (A) to resin (B) is below the upper limit, it is preferable from the viewpoint of excellent flame retardancy of the 3D molded material, and if it is above the lower limit, it is preferable from the viewpoint of more effectively obtaining the effects of the present invention.

[0060] [Other Components] The three-dimensional molding material of the present invention may contain other components besides resin (A) and resin (B), to the extent that it does not impair the purpose of the three-dimensional molding material of the present invention. Other components include additives such as plasticizers and stabilizers that are usually used in combination with polyvinyl chloride resins, and other resins other than resin (A) and resin (B).

[0061] <Plasticizers> Plasticizers are components that impart appropriate fluidity to three-dimensional molding materials during melting. As plasticizers, one or more plasticizers can be arbitrarily selected and used from the known plasticizers exemplified below, in combination.

[0062] Suitable plasticizers include phthalate ester plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, or phthalate esters of higher alcohols or mixed alcohols with approximately 10 to 13 carbon atoms; di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azele Aliphatic dibasic acid ester plasticizers such as tri-2-ethylhexyl trimellitate, dibutyl sebacate, di-2-ethylhexyl sebacate; trimellitate acid ester plasticizers such as tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, di-n-octyl-n-decyl trimellilate; tributyl phosphate, tricresyl phosphate, triphenyl phosphate, trixylyl phosphate, trioctyl Examples of plasticizers include phosphate ester plasticizers such as trichloropropyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, tris(bromochloropropyl) phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropyl phosphate, and bis(chloropropyl) monooctyl phosphate; biphenyltetracarboxylic acid tetraalkyl ester plasticizers such as tetraheptyl 2,3,3',4'-biphenyltetracarboxylic acid; polyester polymer plasticizers; epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, and liquid epoxy resins; chlorinated paraffin; and chlorinated fatty acid esters such as alkyl stearate pentachloride.

[0063] Of these, from the viewpoint of good compatibility with polyvinyl chloride resins or chlorinated polyvinyl chloride resins, it is preferable to use a plasticizer having a polar group, and more preferably phthalate ester plasticizers, aliphatic dibasic acid ester plasticizers, trimellitic acid ester plasticizers, epoxy plasticizers, and polyester polymer plasticizers are preferred because they have good plasticization efficiency and bleed resistance.

[0064] When the three-dimensional molding material of the present invention contains a plasticizer, the plasticizer content is preferably 0.1 to 30 parts by mass, particularly 1 to 15 parts by mass, per 100 parts by mass of resin (A). If the plasticizer content is above the lower limit, a melt viscosity suitable for three-dimensional molding can be obtained. If an excessive amount of plasticizer is included, the solidification characteristics during cooling may be impaired. A plasticizer is not necessarily required, and the three-dimensional molding material of the present invention may not contain a plasticizer.

[0065] <Stabilizers> Stabilizers are effective in improving the thermal stability of polyvinyl chloride resins and include, but are not limited to, one or more of the following: inorganic salts such as tribasic lead sulfate, lead silicate, and basic lead carbonate; metal soaps mainly composed of organic acid salts of metals such as lead, cadmium, barium, calcium, and zinc; fatty acid complexes such as Ba-Zn, Ca-Zn, and Cd-Ba, or fatty acid (phosphite)-based and carboxylate (phosphite)-based complex metal soaps or complex liquid metal soaps; and organotin compounds.

[0066] When the three-dimensional molding material of the present invention contains a stabilizer, the amount of stabilizer is preferably 0.1 to 30 parts by weight, and particularly 1 to 15 parts by weight, per 100 parts by weight of resin (A), from the viewpoint of improving the thermal stability of resin (A).

[0067] <Processing Aids> The three-dimensional molding material of the present invention may contain a methyl methacrylate copolymer such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA") as a processing aid. By including these processing aids, the amount of molten resin discharged from the extrusion nozzle can be stabilized. Preferably, the methyl methacrylate copolymer is a copolymer of methyl methacrylate and an acrylic acid ester. Examples of acrylic acid esters copolymerized with methyl methacrylate include one or more methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate. Furthermore, one or more methacrylic acid esters other than methyl methacrylate, such as ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate, may also be copolymerized.

[0068] If the three-dimensional molding material of the present invention contains these processing aids, the content is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of resin (A). If the content of the processing aid is above the lower limit, the above effects due to the inclusion of the processing aid can be effectively obtained. On the other hand, if the content of the processing aid exceeds the upper limit, it may inhibit the discharge of molten resin from the extrusion nozzle.

[0069] <Other Additives> The three-dimensional molding material of the present invention may contain, to the extent that it does not impair the effects of the present invention, various additives other than those listed above, such as inorganic fillers, freshness preservatives, antibacterial agents, lubricants, plasticizers, antistatic agents, antioxidants, light stabilizers, ultraviolet absorbers, dyes, pigments, hydrolysis inhibitors, crystal nucleating agents, antiblocking agents, lightfastness agents, plasticizers, heat resistance improvers, flame retardants, mold release agents, antifogging agents, surface wetting improvers, incineration aids, dispersion aids, various surfactants, slip agents, and other animal / plant material fine powders such as starch, cellulose, paper, wood flour, chitin / chitosan, coconut shell powder, and walnut shell powder. These may be used individually or in combination of two or more.

[0070] The content of these other additives is usually preferably 0.01 to 40% by mass of the total amount of additives mixed with the three-dimensional material of the present invention, in order not to impair the physical properties of the three-dimensional material of the present invention.

[0071] (Inorganic Filler) The three-dimensional molding material of the present invention may contain an inorganic filler from the viewpoint of making layer lines less noticeable and improving the appearance of the molded object, from the viewpoint of improving the elastic modulus of the filament or pellet to improve handling, and from the viewpoint of assisting solidification during cooling. Examples of inorganic fillers include anhydrous silica, mica, talc, titanium dioxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, wollastonite, calcined perlite, silicates such as calcium silicate and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate and calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate and barium sulfate, and preferably talc, calcium carbonate and zeolite.

[0072] Inorganic fillers can also be classified by their shape. Inorganic fillers can be fibrous, granular, plate-like, or needle-like, with granular and plate-like fillers being preferred, and plate-like fillers being particularly preferred. Examples of plate-like fillers include talc, kaolin, mica, clay, sericite, glass flakes, synthetic hydrotalcite, various metal foils, graphite, molybdenum disulfide, tungsten disulfide, boron nitride, plate-like iron oxide, plate-like calcium carbonate, plate-like aluminum hydroxide, and zeolite. From the viewpoint of ease of compounding, rigidity, moldability, decomposability, improved moisture permeability (such as water vapor), and enhanced deodorizing effect, it is preferable to use talc, mica, or clay, calcium carbonate, or zeolite. Furthermore, the filler may be surface-treated to improve compatibility with the resin and to suppress clumping during molding and sap buildup during filament spinning.

[0073] From a handling standpoint, the inorganic filler preferably has an average particle diameter of 0.5 μm or more, more preferably 0.6 μm or more, even more preferably 0.7 μm or more, and particularly preferably 1.0 μm or more. On the other hand, the average particle diameter of the inorganic filler is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less.

[0074] The method for measuring the average particle size of inorganic fillers is not particularly limited. A specific example of a measurement method is to determine the specific surface area per gram of powder measured using a Shimadzu SS-100 powder specific surface area analyzer (constant pressure air permeation method), and then calculate the average particle size of the filler from the specific surface area measurement results using the air permeation method in accordance with JIS M8511, using the following formula: Average particle size (μm) = 10000 × {6 / (Specific gravity of filler × Specific surface area)}

[0075] Inorganic fillers may be used individually or in combination of two or more types in any combination and ratio.

[0076] Suitable talc products that can be used as inorganic fillers include, for example, Microace from Nippon Talc Corporation and MG113 and MG115 from Fuji Talc Industries Co., Ltd. Specific examples of calcium carbonate products that can be used as inorganic fillers include Softon 1200 and 2200 from Bihoku Funka Kogyo Co., Ltd.

[0077] When the three-dimensional molding material of the present invention contains an inorganic filler, the percentage of the inorganic filler is not particularly specified, but it is preferably 1 to 60% by mass, more preferably 2 to 30% by mass, and even more preferably 5 to 25% by mass, relative to the total amount of the three-dimensional molding material of the present invention. If the percentage of inorganic filler is less than the lower limit above, the effect of improving the appearance of the molded object cannot be sufficiently obtained. On the other hand, if the percentage of inorganic filler is more than the upper limit above, there is a concern that it will inhibit the interlayer adhesion of the molded object and the strength of the molded object will be inferior.

[0078] In the case of the 3D modeling material of the present invention, especially when it contains the above-mentioned inorganic filler, a dispersant may be added to suppress clumping that occurs when inorganic filler bleeds from the resin onto the extrusion nozzle during modeling, and to suppress smearing during the production of the modeling material. Examples of such dispersants include metal soaps (metal fatty acid salts), fatty acid esters, fatty acid amides, waxes, and low molecular weight polymers. Among these, metal soaps such as calcium stearate and magnesium stearate are preferred from the viewpoint of dispersibility and bleed suppression. The amount of these dispersants added is preferably 0.001 to 5% by weight relative to the total amount of the 3D modeling material of the present invention.

[0079] (Anti-fogging agent) Specifically, as an anti-fogging agent, an ester-type surfactant of a saturated or unsaturated aliphatic carboxylic acid having 4 to 20 carbon atoms and a polyhydric alcohol is preferably used. These can be blended as desired within a range that does not impair the effects of the present invention, and one type may be used alone or two or more types may be used in combination.

[0080] (Slip agent) Examples of slip agents include unsaturated and saturated fatty acid amides and unsaturated and saturated fatty acid bisamides, which consist of unsaturated and saturated fatty acids having 6 to 30 carbon atoms. Most preferably, slip agents include erucic acid amide, oleic acid amide, stearic acid amide, and their bisamides. These can be arbitrarily blended within a range that does not impair the effects of the present invention, and one type may be used alone or two or more types may be used in mixture.

[0081] (Antiblocking agents) Examples of antiblocking agents include saturated fatty acid amides having 6 to 30 carbon atoms, saturated fatty acid bisamides, methylolamides, ethanolamides, natural silica, synthetic silica, synthetic zelite, talc, etc. These can be arbitrarily blended within a range that does not impair the effects of the present invention, and one type may be used alone or two or more types may be used in combination.

[0082] (Lightfastness agents) Specifically, the lightfastness agents include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-n-butyl-bis(2,2,6,6-tetramethyl-4-piperidyl) malonate, and 2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-n-butyl-bis(1,2,2,6,6-pentamethyl-4 -Piperidyl) malonate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl-bis(2,2,6,6-tetramethyl-4-piperidyl) malonate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl-bis(1,2,2,6,6-pentamethyl-4-piperidyl) malonate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane Tetracarboxylate, mixed (2,2,6,6-tetramethyl-4-piperidyl / tridecyl)-1,2,3,4-butanetetracarboxylate, mixed (1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl)-1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl-4-piperidyl / β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro[5.5]undecane]diethyl}-1,2,3,4-butanetetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro[5.5]undecane]diethyl}-1,2,3,4-butanetetracarboxylate, 1,2-bis(3-oxo-2,2,6,6-tetramethyl-4-piperidyl)ethane, 1-(3,5-di-t-butyl-4-hydroxyphenyl)-1,1-bis(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)pentane, poly[1-oxyethylene(2,2,6,6-tetramethyl-1,Examples include [4-piperidyl)oxysuccinyl], poly[2-(1,1,4-trimethylbutylimino)-4,6-triazinediyl-(2,2,6,6-tetra and-4-piperidyl)iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidyl)imino], N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate and its N-methyl compound, polycondensate of succinic acid and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, etc. These can be arbitrarily blended in a range that does not impair the effects of the present invention, and one type may be used alone or two or more types may be used in combination. Among these, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl-bis(1,2,2,6,6-pentamethyl-4-piperidyl) malonate are particularly preferred.

[0083] (UV absorbers) Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylic acid-based, and cyanoacrylate-based UV absorbers. Among these UV absorbers, benzotriazole-based UV absorbers are preferred, specifically 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol. These can be arbitrarily blended within a range that does not impair the effects of the present invention, and one type may be used alone or two or more types may be used in combination.

[0084] (Antioxidants) Antioxidants include BHT (dibutylhydroxytoluene), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,3',3”,5,5',5”,Hexa-tert-butyl-α,α',α”,(mesitylene-2,4,6-triyl)tri-p-cresol, Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3, 5-Tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, calcium diethylbis[{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]phosphonate, bis(2,2'-dihydroxy-3,3'-di-tert-butyl-5,5 Hindered phenol antioxidants such as '-dimethylphenyl)ethane, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl)-4-hydroxyphenyl]propionamide, tridecyl phosphite, diphenyldecyl phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, bis(2,4-di-tert- Examples of antioxidants include phosphorus-based antioxidants such as butylphenyl pentaerythritol diphosphite, lactone-based antioxidants such as reactive compounds of 3-hydroxy-5,7-di-tert-butylfuran-2-one and xylene, and sulfur-based antioxidants such as dilauryl thiodipropionate and distearyl thiodipropionate. These can be arbitrarily blended within a range that does not impair the effects of the present invention, and one or more may be used individually or in combination. Among these, hindered phenol-based antioxidants are preferably used.

[0085] Preferred hindered phenol antioxidants include Irganox® 3790, Irganox 1330, Irganox 1010, Irganox 1076, Irganox 3114, Irganox 1425WL, Irganox 1098, Irganox HP2225FL, Irganox HP2341, Irgaphos® XP-30 (all manufactured by BASF), and Sumirizer® BBM-S (manufactured by Sumitomo Chemical Co., Ltd.). The most preferred antioxidants are Irganox 1010 (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and Irganox 1330 (3,3',3'', 5,5',5'', hexa-tert-butyl-α,α',α'', (mesitylene-2,4,6-triyl)tri-p-cresol).

[0086] <Other Resins> The three-dimensional molding material of the present invention may contain one or more resins other than resin (A) and resin (B), such as aromatic polyester resins, polycarbonate, polyamide, polystyrene (except resin (B)), polyolefin, acrylic resin, amorphous polyolefin, polycaprolactone, polyvinyl alcohol, cellulose ester, and other synthetic resins, as well as biodegradable resins such as polylactic acid and aliphatic aromatic polyester polybutylene adipate terephthalate (PBAT).

[0087] When the three-dimensional molding material of the present invention contains these other resins, in order to effectively obtain the effects of the present invention, it is preferable that the content of the other resins be 20 parts by mass or less, particularly 10 parts by mass or less, and even more preferably 5 parts by mass or less, in the total of 100 parts by mass of resin (A) and resin (B) and the other resins.

[0088] [Flowability of the 3D Modeling Material] The 3D modeling material of the present invention preferably has a melt mass flow rate (MFR) of 1 to 50 g / 10 min, and more preferably 2 to 30 g / 10 min, as measured by the method described in the Examples section below. If the MFR of the 3D modeling material is above the lower limit, it exhibits excellent flowability and material extrusion in 3D modeling. On the other hand, if the MFR of the 3D modeling material is below the upper limit, it is possible to suppress the occurrence of defects such as resin dripping from the extrusion nozzle.

[0089] [Shape of the material for 3D printing] The material for 3D printing of the present invention is characterized by its pellet shape. A pellet-shaped material for 3D printing offers excellent productivity, handling, material extrusion methods, and compatibility, and also allows for a significant improvement in the solidification characteristics during cooling as described in the present invention.

[0090] Examples of pellet-shaped 3D printing materials of the present invention include cylindrical (including those with an elliptical cross-section), prismatic, spherical, rice-grain shaped, disc-shaped, and cube-shaped. Regarding pellet size, from the viewpoint of ensuring good engagement with the screw typically located at the top of the 3D printer nozzle during printing, the length of the longest part of the pellet is preferably 10 mm or less, and more preferably 5 mm or less. Furthermore, from the viewpoint of suppressing entanglement with the screw, the length of the shortest part of the pellet is preferably 0.1 mm or more, and more preferably 0.5 mm or more.

[0091] [Method for Manufacturing Three-Dimensional Modeling Materials] The three-dimensional modeling material of the present invention is manufactured by mixing resin (A) and resin (B) with other components used as needed. From the viewpoint of productivity, it is preferable that all components are mixed during manufacturing.

[0092] This mixing process is carried out by mixing resin (A) and resin (B) and other components used as needed in predetermined proportions simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, or extruder, preferably by melt kneading.

[0093] The kneader used in the mixing process may be a melt extruder. The type of extruder is not limited to a twin-screw extruder or a single-screw extruder, but a twin-screw extruder is more preferable for achieving melt kneading, depending on the characteristics of the resins (A) and (B) used, as well as other components.

[0094] The temperature during melt mixing is preferably 100 to 230°C, and more preferably 130 to 200°C. Within this temperature range, the time required for melt mixing can be shortened, deterioration of color due to resin degradation can be prevented, and practical physical properties such as impact resistance and heat and humidity resistance can be further improved.

[0095] From the perspective of more reliably avoiding resin degradation, the melt-mixing time should not be unnecessarily prolonged; it is preferably 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes. It is preferable to set the melt-mixing temperature and time conditions so as to satisfy this melt-mixing time.

[0096] The pellet-shaped three-dimensional molding material of the present invention can be manufactured, for example, by pelletizing it using any method such as strand cutting or hot cutting during the melt-kneading process described above.

[0097] The three-dimensional molding material of the present invention may be manufactured by the above method, dried overnight at 80°C or higher, and then sealed and stored in an aluminum inner bag or polyethylene bag while maintaining a low moisture content. The moisture content of the molding material after drying is preferably 2.5% or less. More preferably 2.0% or less, even more preferably 1.5% or less, and particularly preferably 1.0% or less. The moisture content may also be 0.3% or higher, or 0.6% or higher. Within this range, foaming and smoke generation during extrusion are reduced, and dimensional stability and mechanical strength are stable, making it preferable. The moisture content is measured by the Karl Fischer method.

[0098] [Formed object] The formed object of the present invention is obtained by forming the three-dimensional forming material of the present invention using a 3D printer, and the formed object of the present invention is formed with an extrusion width of 1 mm or more, preferably 1.5 mm or more, more preferably 2 mm or more, preferably 20 mm or less, and more preferably 15 mm or less.

[0099] [Method for Manufacturing Molded Objects] Molded objects can be manufactured by using the 3D molding material of the present invention and molding it with a 3D printer using the material extrusion method. 3D printers using the material extrusion method are relatively inexpensive to obtain and are preferable from the viewpoint of excellent handling of the 3D molding material. Furthermore, when manufacturing molded objects according to the present invention, a molding material made of another resin may be used simultaneously as a support material, and after the molding is complete, this support material may be removed to obtain the molded object according to the present invention.

[0100] Extrusion-based 3D printers generally consist of a heatable build table, extrusion nozzle, heating and melting chamber, and raw material supply unit. Some of these 3D printers have the extrusion nozzle and heating and melting chamber integrated into a single unit.

[0101] The extrusion nozzle is mounted in a gantry structure, allowing it to be moved arbitrarily on the X-Y plane of the build table. The build table is the platform for constructing the desired object and support material, and it is preferable that it be designed to allow for heating and maintaining temperature to achieve adhesion with the object and improve the dimensional stability of the resulting object as a desired three-dimensional object. Typically, at least one of the extrusion nozzle and the build table is movable in the Z-axis direction perpendicular to the X-Y plane. In addition, some printers have a design where the nozzle moves only in the X direction (or Y direction), and the build table moves in the Y direction (or X direction).

[0102] The pellet-shaped 3D molding material of the present invention is fed in from a raw material supply unit such as a quantitative feeder or hopper, melts, and is sent to an extrusion nozzle by a screw or piston, and then extruded from the tip of the extrusion nozzle.

[0103] Specifically, as shown in Figure 1, a 3D printer is used that has a hopper (raw material supply unit) 1, a cylinder 2 which is a melting and extruding unit for the supplied raw material, and an extruder 10 equipped with an extrusion nozzle 5 for molten resin. Resin pellets 6, which are the pellet-shaped 3D molding material of the present invention, are fed from the hopper 1. Inside the cylinder 2, there is a screw 4 for feeding the fed-in resin pellets 6 towards the extrusion nozzle 5, and a heater 3 for heating the resin pellets 6 inside the cylinder 2. As a result, the resin pellets 6 fed from the hopper 1 into the cylinder 2 flow inside the cylinder 2 while being heated and melted, and are extruded in a strand-like manner from the extrusion nozzle 5 to form a molded object 20.

[0104] The 3D modeling material extruded from the extrusion nozzle is deposited onto the build plate by the movement of the extrusion nozzle or build plate based on a signal transmitted from the 3D model. After this process is complete, the deposited material is removed from the substrate, and support materials and other excess parts are removed as needed to obtain the desired 3D object.

[0105] The temperature of the molten resin discharged from the extrusion nozzle is preferably 120°C or higher, more preferably 150°C or higher, while it is preferably 220°C or lower, and more preferably 200°C or lower. When the temperature of the molten resin is above the lower limit, the resin flows sufficiently, which tends to result in a superior molded appearance even when molded at high speed, and is therefore preferable. On the other hand, when the temperature of the molten resin is below the upper limit, it is preferable because it is easier to prevent problems such as thermal decomposition of the resin, burning, smoke, odor, stickiness, and clumping.

[0106] The diameter of the extrusion nozzle that extrudes the molding material (the inner diameter of the extrusion opening of the extrusion nozzle) is preferably 0.5 mm or more, more preferably 1 mm or more, even more preferably 1.5 mm or more, particularly preferably 2 mm or more, preferably 20 mm or less, more preferably 15 mm or less, and even more preferably 10 mm or less. Using an extrusion nozzle of such diameter, the molding material is extruded in strand form with a diameter of preferably 0.5 mm or more, more preferably 1 mm or more, even more preferably 1.5 mm or more, particularly preferably 2 mm or more, preferably 20 mm or less, more preferably 15 mm or less, and even more preferably 10 mm or less. When the molding material is extruded from the nozzle in such a shape, it is preferable because it is excellent in terms of the productivity of the molded object and the extruded resin is also easily cooled appropriately.

[0107] In this 3D printing process, the object produced by the present invention is manufactured with an extrusion width of 1 mm or more. That is, the effect of improving the solidification characteristics during cooling by the 3D printing material of the present invention is particularly evident when performing 3D printing with a wide extrusion width of 1 mm or more. In such printing, the layer pitch is usually 0.3 mm or more, and the 3D printing material of the present invention can produce good 3D objects even with such a thick layer pitch. Here, the layer pitch corresponds to the height W of each layer of the object 20 in Figures 1(a) and (b). The extrusion width, as shown in Figure 1(b), corresponds to the width (length in the direction perpendicular to the layering direction) of the cross-section in the layering direction (up and down direction in Figures 1(a) and (b)) of the strand-like material that is extruded from the extrusion nozzle 5 and layered on the build table to form the object 20. By performing 3D printing with such a wide extrusion width and thick layer pitch W, production efficiency is greatly improved. From this viewpoint, a discharge width of 1.5 mm or more, particularly 2 mm or more, and a layering pitch W of 0.5 mm or more, particularly 0.8 mm or more, are preferred. On the other hand, if the discharge width or layering pitch is excessively large, cooling and solidification becomes extremely difficult, so from the viewpoint that the discharge width is preferably 20 mm or less, more preferably 15 mm or less, and the layering pitch W is preferably 10 mm or less, more preferably 5 mm or less.

[0108] [Applications of the molded objects] The molded objects of the present invention can be suitably used in a wide range of applications, from small to large, including stationery, toys, food containers, agricultural materials, medical components, school teaching materials, home appliances, repair parts for office automation equipment, various parts for automobiles, motorcycles, bicycles, aircraft, etc., and building materials.

[0109] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the essence of the invention.

[0110] [Raw Materials Used] The raw materials used in the following examples and comparative examples are as follows:

[0111] Resin (A): Vinyl chloride resin with an average degree of polymerization of 500. Resin (B)-1: ABS ("Clarastick® S-3820" manufactured by A&L Japan Co., Ltd.), Shore hardness: D82, MVR: 6cm ３ / 10-minute resin (B)-2: SAN ("UMG AXS Resin (registered trademark) S101S" manufactured by Techno UMG Co., Ltd.), Shore hardness: D86, MVR: 18cm ３ / 10-minute resin (B)-3: ASA High Flow (Unibright® UA-1200 manufactured by A&L Japan Co., Ltd.), Shore hardness: D78, MVR: 40cm ３ / 10-minute resin (B)-4: ASA standard ("Unibright® UA-1300" manufactured by A&L Japan Co., Ltd.), Shore hardness: D78, MVR: 20cm ３ Plasticizer: Diisononyl phthalate (DINP) / 10 minutes Plasticizer: Elastren® 404FB manufactured by Resonaq Holdings Co., Ltd. Ca / Zn stabilizer: Ca / Zn stabilizer manufactured by Mizusawa Chemical Industry Co., Ltd. MBS rubber: Kaneka Corporation's Kaneace® B-564, Shore hardness: A87 PMMA: Kaneka Corporation's Kaneace® PA20

[0112] [Measurement and Evaluation Methods] The various physical properties and measurement and evaluation methods for the 3D modeling materials manufactured in the following examples and comparative examples are as follows.

[0113] <Flame Retardancy> Using the manufactured pellets, test specimens molded to 125 x 13 x t3 (mm) by injection molding were subjected to flame retardancy tests using a method compliant with UL94V, and the flame retardancy was evaluated as follows based on the results: Excellent: V-0 and total flaming burn time less than 10 seconds Good: V-0 and total flaming burn time between 10 seconds and 20 seconds Not good: V-0 but total flaming burn time longer than 20 seconds Bad: V-1

[0114] <Fluidity (MFR)> For the manufactured pellets, the melt mass flow rate (MFR) was measured in accordance with JIS 7210 (ISO 1133) using a melt mass flow rate measuring device (manufactured by Tateyama Kagaku Kogyo, device name: Melt Indexer) at 200°C and a load of 2.16 kg.

[0115] <Fan-off buildability (solidification characteristics during cooling after extrusion from nozzle)> Using the manufactured pellets, a 35cm square cylinder was printed in spiral mode on a pellet 3D printer (Tumaker "BIGFootPro Pellets") under the following printing conditions: Nozzle diameter: 2mm Nozzle temperature: 200℃ Extruder temperature: 200℃ Table temperature: 60℃ Printing speed: 5mm / s Extrusion width: 3.5mm Layer thickness: 1mm Cooling fan: OFF The solidification characteristics during cooling were judged as follows from the appearance of the printed object when printed to a target height of 35cm: Good: The appearance of the printed object was less likely to collapse, and a good appearance was achieved even at more than 50% of the print volume (height of the printed object of 17.5cm or more). Average: The appearance of the printed object deteriorated and it was deemed a defective print when 45% to less than 50% of the print was completed (height of the printed object 15.75 cm to less than 17.5 cm). Not good: The appearance of the printed object deteriorated and it was deemed a defective print when 40% to less than 45% of the print was completed (height of the printed object 14 cm to less than 15.75 cm). Bad: The appearance of the printed object deteriorated and it was deemed a defective print when less than 40% of the print was completed (height of the printed object less than 14 cm).

[0116] <Impact Resistance of the Molded Object> The impact resistance of the molded object was evaluated as follows based on its condition when dropped from a height of 1.5m onto a concrete surface. Good: No chips or cracks were observed in the molded object. Average: Minor cracks and chips were observed, but not visible to the naked eye. Bad: Chips and cracks were observed in the molded object.

[0117] <Interlayer Adhesion of Printed Objects> Except for turning on the cooling fan, the objects were fabricated under the same conditions as when evaluating the printability with the fan off. The ease with which the layered surface could be peeled off the top surface of the obtained object with a finger was evaluated as follows: Good: The layered surface could not be peeled off with a finger. Average: Part of the layered surface could be peeled off with a finger. Bad: The layered surface could be easily peeled off with a finger.

[0118] [Example 1] Resin (A), resin (B)-1, plasticizer, Ca / Zn stabilizer, and PMMA were blended in the proportions shown in Table 1, stirred in a high-speed mixer until it reached 100°C, and then discharged. The discharged mixture was kneaded in a melt kneader using a φ40 mm single-screw extruder (cylinder temperature: 140-160°C, die temperature: 160°C, screw rotation speed: 30 rpm), and the strand extruded from a nozzle with a diameter of 3 mm was cut to obtain cylindrical pellets with a diameter of approximately 4 mm and a height of approximately 4 mm. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0119] [Example 2] Pellets were obtained in the same manner as in Example 1, except that the amount of resin (B)-1 was changed as shown in Table 1. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0120] [Example 3] Pellets were obtained in the same manner as in Example 2, except that no plasticizer was added. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0121] [Example 4] Pellets were obtained in the same manner as in Example 1, except that the amount of resin (B)-1 was changed as shown in Table 1. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0122] [Example 5] Pellets were obtained in the same manner as in Example 2, except that resin (B)-1 was changed to resin (B)-2. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0123] [Example 6] Pellets were obtained in the same manner as in Example 2, except that resin (B)-1 was changed to resin (B)-3. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0124] [Example 7] Pellets were obtained in the same manner as in Example 2, except that resin (B)-1 was changed to resin (B)-4. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0125] [Example 8] Pellets were obtained in the same manner as in Example 1, except that the amount of resin (B)-1 was changed as shown in Table 1. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0126] [Comparative Example 1] Pellets were obtained in the same manner as in Example 1, except that resin (B) was not included. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0127] [Comparative Example 2] Pellets were obtained in the same manner as in Comparative Example 1, except that MBS-based rubber was further added to the formulation of Comparative Example 1. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0128] [Comparative Example 3] Chlorinated PE was used instead of resin (B), and pellets were obtained in the same manner as in Example 1 using the formulation shown in Table 1. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0129] [Comparative Example 4] Pellets were obtained in the same manner as in Example 1, except that the amount of resin (B)-1 was changed as shown in Table 1. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0130] [Comparative Example 5] Pellets were obtained in the same manner as in Example 1, except that the amount of resin (B)-1 was changed as shown in Table 1. Various evaluations were performed on these pellets. The results are shown in Table 1.

[0131]

[0132] Table 1 shows the following: Examples 1 to 7 are within the scope of the present invention, and therefore exhibit excellent solidification characteristics during cooling after extrusion from the nozzle, as well as excellent flame retardancy and impact resistance and interlayer adhesion of the resulting molded objects. Example 8 exhibits excellent flame retardancy. Furthermore, since it contains a sufficient amount of resin (B), it is considered that the solidification characteristics during cooling after extrusion from the nozzle, as well as the impact resistance and interlayer adhesion of the resulting molded objects, are as excellent as those of Examples 1 to 7. On the other hand, Comparative Examples 1 to 3 do not contain resin (B), and therefore exhibit inferior solidification characteristics during cooling, as well as inferior impact resistance and interlayer adhesion of the resulting molded objects. Comparative Example 2 adds MBS-based rubber instead of resin (B), and exhibits excellent impact resistance of the molded object, but the solidification characteristics during cooling are not improved from Comparative Example 1. Comparative Example 3 adds chlorinated PE instead of resin (B), but no effect of improving the solidification characteristics during cooling is observed, and the interlayer adhesion of the resulting molded object is also inferior. The poor interlayer adhesion of the molded objects is thought to be due to the fact that chlorinated PE is a crystalline resin, and the crystallization of the resin inhibits interlayer adhesion. Furthermore, comparative examples 4 and 5 have inferior flame retardancy because the content of resin (B) is outside the scope of the present invention.

[0133] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications are possible within the scope of achieving the effects of the invention. This application is based on Japanese Patent Application No. 2024-166465, filed on 25 September 2024, which is incorporated herein by reference in its entirety.

[0134] 1. Hopper 2. Cylinder 3. Heater 4. Screw 5. Extrusion nozzle 6. Resin pellets 10. Extruder 20. Printed object

Claims

1. A pellet-shaped three-dimensional molding material comprising the following resin (A) and resin (B), wherein the amount of resin (B) is 0.1 to 50 parts by mass per 100 parts by mass of resin (A). Resin (A): At least one resin from polyvinyl chloride resin and chlorinated polyvinyl chloride resin. Resin (B): Styrene copolymer resin having a Shore hardness of A90 or higher.

2. The three-dimensional molding material according to claim 1, wherein the average degree of polymerization of the resin (A) is 3800 or less.

3. The three-dimensional molding material according to claim 1, wherein the resin (B) is at least one selected from the group consisting of acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, acrylonitrile-ethylenepropylene-styrene resin, methyl methacrylate-butadiene-styrene resin, butadiene-styrene resin, and acrylate-styrene-acrylonitrile resin.

4. The three-dimensional molding material according to claim 1, wherein the total content ratio of resin (A) and resin (B) is 50% by mass or more.

5. The material for three-dimensional molding according to claim 1, wherein the mass ratio of the amount of resin (A) to resin (B) blended [resin (B)] / [resin (A)] is 0.01 or more and 0.3 or less.

6. The three-dimensional molding material according to claim 1, wherein the resin (B) comprises 50 to 90% by mass of aromatic vinyl monomer units and 10 to 50% by mass of one or more of the following: vinyl cyanide monomer units, rubbery polymer units, and other monomer units.

7. The melt volume rate of resin (B), measured in accordance with ISO 1133 under conditions of 220°C and 10 kgf, is between 1 and 100 cm². ３ The material for three-dimensional molding according to claim 1, which has a lifespan of 10 minutes.

8. The three-dimensional molding material according to claim 1, wherein the melt mass flow rate of the three-dimensional molding material, measured at 200°C and a load of 2.16 kg in accordance with JIS 7210 (ISO 1133), is 1 to 50 g / 10 min.

9. A molded object formed by molding a three-dimensional molding material according to any one of claims 1 to 8 using a three-dimensional printer, wherein the extrusion width during molding is 1 mm or more.

10. A method for manufacturing a molded object, comprising the step of extruding a pellet-shaped three-dimensional molding material from an extrusion nozzle, comprising the following resin (A) and the following resin (B), wherein the amount of resin (B) is 0.1 to 50 parts by mass per 100 parts by mass of resin (A). Resin (A): At least one resin from polyvinyl chloride resin and chlorinated polyvinyl chloride resin. Resin (B): Styrene copolymer resin having a Shore hardness of A90 or higher.

11. The method for manufacturing a molded object according to claim 10, wherein, in the step of extruding the three-dimensional molding material from an extrusion nozzle, the temperature of the molten resin extruded from the extrusion nozzle is 120°C or higher and 220°C or lower.

12. The method for manufacturing a molded object according to claim 10, wherein, in the step of extruding the three-dimensional molding material from an extrusion nozzle, the diameter of the extrusion nozzle is 0.5 mm or more and 20 mm or less.

13. The method for manufacturing a molded object according to claim 10, wherein the step of extruding the three-dimensional molding material from an extrusion nozzle is a step of using a three-dimensional printer equipped with a raw material supply unit, a melting and extruding unit for the supplied raw material, and an extrusion nozzle for extruding molten resin, in which the three-dimensional molding material introduced from the raw material supply unit is fed to the extrusion nozzle while being melted, and extruded from the extrusion nozzle.

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