3D modeling resin composition

Abstract

The present invention provides a material for 3D printing and a printed object made using the same, which can suppress deformation such as warping as a measure of shape accuracy of 3D printed objects, while also balancing external shape, interlayer adhesion strength, and mechanical properties other than shape accuracy. [Solution] A resin composition for 3D modeling comprising (Ai) a propylene-based random copolymer (A) containing propylene and ethylene or at least one of an olefin having 4 to 10 carbon atoms, having a melting peak temperature of 110°C to 150°C, (A-ii) a heat of fusion of 80 J / g or less, and (A-iii) a melt flow rate (MFR) of 0.1 g / 10 min to 15 g / 10 min, a filler (B) which is at least one of an inorganic filler or an organic filler, and a compatibilizer (C), wherein when the total weight of (A) and (B) is 100% by weight, (A) is present in an amount of 40% by weight or more, and when the total weight of (A) and (B) is 100 parts by weight, (C) is present in an amount of 0.1 parts by weight or more.

Description

Technical Field

[0001] The present invention relates to a resin composition for three-dimensional shaping and a shaped object thereof.

Background Art

[0002] Three-dimensional shaping (3D printing) is a technology for manufacturing three-dimensional objects based on three-dimensional model data created by a computer. Different from molding with a mold or shaping by cutting, it does not require a mold or a cutting tool, can immediately respond to frequent design changes, and can shape hollow shapes and complex internal shapes. Therefore, three-dimensional shaping technology is rapidly spreading in a wide range of fields as a technology that can efficiently perform shaping.

[0003] In general, three-dimensional shaping techniques are performed by laminating cross-sectional shapes of three-dimensional model data (for example, Patent Document 1), and are collectively called Additive manufacturing, including various lamination methods. The basic principle is to cure a resin with fluidity during shaping. There are methods such as the material extrusion (MEX) method, the stereolithography method, the inkjet method, the powder adhesion shaping method, and the powder sintering shaping method. In particular, the material extrusion method is easy to use because it does not require additional equipment and allows a wide range of material selection. The material extrusion method is a method of creating a three-dimensional shape by melting a thermoplastic resin processed into pellets or filaments and laminating it while extruding it (Patent Document 2). Engineering plastics such as ABS resin and polycarbonate can be used, and shaped objects can be manufactured according to the characteristics of each engineering plastic. Since the operability of molding with a three-dimensional shaping device (3D printer) changes depending on the physical properties of the resin, various resins have been tried as resins for 3D printers (Patent Documents 3 to 5).

[0004] Focusing on crystalline resins such as polypropylene as the resin for 3D printers, in shaping methods that laminate and cool molten resins, such as the material extrusion method, warping may occur due to shrinkage accompanying the temperature drop of the molten resin, and the dimensions of the shaped object may not match the 3D model data. As means to solve this problem, in addition to blending components of inorganic fillers such as glass fibers into polypropylene (Patent Document 6), the compatibility of the interlayer adhesion force and mechanical properties of three-dimensional objects by the combined use of inorganic fillers and α-olefin elastomers has been achieved (Patent Document 7).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Summary of the Invention

Problems to be Solved by the Invention

[0006] From the above prior art, it is recognized that polypropylene containing inorganic fillers is suitable for obtaining molded objects with minimal warping and deformation because the shrinkage of the resin is suppressed. However, when using fillers with large particle sizes or when the filler concentration is high, the surface of the resin extruded from the nozzle may become rough, and molded objects with smooth surfaces may not be obtained. For example, when using fibrous fillers, it has been newly discovered that, as shown in the comparative example described later, fine irregularities occur on the surface of the molded object, and fibers may protrude, causing fuzziness, resulting in problems with appearance and tactile properties other than deformation such as warping. Such problems are not disclosed at all in the above prior art documents.

[0007] The problem that the present invention aims to solve is to provide a material for 3D printing that exhibits minimal deformation such as warping (shape accuracy) as a 3D molded object, and a balanced combination of other external shapes, inter-layer resin adhesion, and mechanical properties. The problem that other embodiments of the present invention aim to solve is to provide a 3D molded object and a method for manufacturing the same that exhibits a balanced combination of shape accuracy, external shape, inter-layer resin adhesion, and mechanical properties as a 3D molded object. [Means for solving the problem]

[0008] The inventors have found that the above problems can be solved by using a propylene-based resin composition that satisfies certain conditions. Although technologies are being developed to suppress deformation such as warping when using polypropylene, a crystalline resin, for 3D printing applications, no technology has been found to improve the external shape accuracy. The present invention was developed by finding that it is possible to suppress deformation such as warping in 3D printed objects using polypropylene while balancing external shape accuracy other than shape accuracy, inter-layer resin adhesion, and mechanical properties.

[0009] In other words, the present invention relates to the following items. [1] A propylene-based random copolymer (A) having the following properties (Ai) to (A-iii), containing propylene and at least one of ethylene or an olefin having 4 to 10 carbon atoms, A filler (B) which is at least one of an inorganic filler or an organic filler, and Contains compatibilizer (C), When the total weight of the propylene-based random copolymer (A) and the filler (B) is taken as 100% by weight, (A) is 40% to 99% by weight, and (B) is 1% to 60% by weight, A resin composition for three-dimensional molding, characterized in that it contains (C) in an amount of 0.1 parts by weight or more when the total weight of (A) and (B) is 100 parts by weight. Characteristics (Ai): The melting peak temperature measured by DSC method is 110°C to 150°C. Characteristic (A-ii): The heat of fusion measured by the DSC method is 80 J / g or less. Characteristics (A-iii): The melt flow rate (MFR) at 230°C and a load of 2.16 kg is 0.1 g / 10 min to 15 g / 10 min. [2] The resin composition for three-dimensional molding according to [1], characterized in that the filler (B) is at least one selected from talc, calcium carbonate, calcined kaolin, glass fiber, wood powder, cellulose powder, carbon fiber, and cellulose fiber. [3] The resin composition for three-dimensional molding according to [1] or [2], characterized in that the compatibilizer (C) is at least one selected from acid-modified polyolefins and hydroxy-modified polyolefins. [4] A resin composition for three-dimensional molding according to any one of [1] to [3], characterized in that the filler (B) is fibrous, and the copolymer (A), the filler (B), and the compatibilizer (C) are melt-kneaded at 200°C, a screw rotation speed of 300 rpm, and a discharge rate of 21 kg / hour, and after cooling, the average length of the filler (B) measured with a digital microscope is 0.1 mm or more and 2.5 mm or less. [5] A resin composition for three-dimensional molding according to any one of [1] to [4], characterized in that the filler (B) is glass fiber. [6] A three-dimensional object comprising the resin composition for three-dimensional molding described in any of [1] to [5] above. [7] A method for producing a resin composition for three-dimensional molding according to any of [1] to [5] above, characterized by comprising the step of melt-kneading a propylene-based random copolymer (A), a filler (B), and a compatibilizer (C) to obtain a melt-kneaded resin composition. [8] A method for manufacturing a three-dimensional object, characterized by comprising a method for manufacturing the resin composition for three-dimensional molding described in [7] above. [9] A method for manufacturing a three-dimensional object according to [8], characterized by comprising the steps of supplying the molten-mixed resin composition to the raw material supply section of a three-dimensional object manufacturing apparatus, melting it in the heating section of the three-dimensional object manufacturing apparatus, extruding it from a nozzle which is the discharge section of the three-dimensional object manufacturing apparatus, and building a three-dimensional object by layering the extruded resin composition. [Effects of the Invention]

[0010] According to the present invention, a material for 3D modeling and a model made using the same are provided, which can suppress deformation such as warping as a measure of shape accuracy of 3D modeled objects, while also balancing external shape, interlayer adhesion strength, and mechanical properties other than shape accuracy. [Modes for carrying out the invention]

[0011] The present invention relates to a resin composition for three-dimensional molding, comprising a propylene-based random copolymer, a filler, and a compatibilizer, and a molded object using the resin. The resin composition used in the present invention has the characteristics of high transparency and a low melting point because it contains a propylene-based random copolymer.

[0012] The resins constituting the present invention will be described in detail below, item by item. In this specification, "(meth)acrylic acid" and "(meth)acrylate" mean acrylic acid or methacrylic acid, or "acrylate" or "methacrylate." Also, in this specification, "~" indicating a numerical range is used to mean that the values ​​written before and after it are included as the lower and upper limits.

[0013] 1.Copolymer (A) Copolymer (A) is a propylene-based random copolymer containing propylene and at least one of ethylene or an olefin having 4 to 10 carbon atoms (hereinafter, with respect to copolymer (A), ethylene and olefins having 4 to 10 carbon atoms may be referred to as "comonomers"), and is a copolymer having the properties specified in (Ai) to (A-iii) below. Characteristics (Ai): The melting peak temperature measured by DSC method is 110°C to 150°C. Characteristic (A-ii): The heat of fusion measured by the DSC method is 80 J / g or less. Characteristics (A-iii): The melt flow rate (MFR) at 230°C and a load of 2.16 kg is 0.1 g / 10 min to 15 g / 10 min.

[0014] Copolymer (A) is a propylene-based random copolymer containing propylene and at least one of ethylene or an olefin having 4 to 10 carbon atoms. The comonomer of copolymer (A) is selected to be ethylene or an olefin having 4 to 10 carbon atoms. The olefin having 4 to 10 carbon atoms may be linear or branched, and may contain a cyclic structure in part. Specific examples of olefins having 4 to 10 carbon atoms include linear olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, and 1-decene; branched olefins such as 4-methyl-1-pentene; and cyclic olefins such as cyclohexene and norbornene. However, the copolymer is not limited to these as long as the carbon number requirement is met. As the comonomer, ethylene or linear α-olefins having 4 to 10 carbon atoms are preferred, and ethylene, 1-butene, and 1-hexene are more preferred. Furthermore, two or more comonomers may be used in combination.

[0015] Copolymer (A) is obtained by randomly copolymerizing propylene with ethylene or at least one olefin having 4 to 10 carbon atoms. A random copolymer is a copolymer in which the probability of finding each monomer structural unit at any given position in a molecular chain is independent of the type of adjacent structural unit. The random copolymerizability of a copolymer can be confirmed by various methods and is known to those skilled in the art.

[0016] Polypropylene has structural units represented by -CH2-CH(CH3)-, so the structure formed by linking two propylene units can be either continuous methylene groups or alternating methylene groups. Furthermore, carbon atoms to which methyl groups are bonded in the polymer chain become chiral carbon atoms. For this reason, the relative positional relationship of two methyl groups between adjacent structural units is considered in polypropylene. This stereoregularity can be described in three states: isotactic, syndiotactic, and atactic. In copolymer (A), a polypropylene portion that is not interrupted by comonomer units can be assumed, and this portion may be in any of these states.

[0017] The comonomer content in copolymer (A) may be greater than 0% by weight and 13.0% by weight or less. The upper limit of the comonomer content in copolymer (A) may be 12.0% by weight or less, 11.0% by weight or less, 10.0% by weight or less, 5.0% by weight or less, 4.0% by weight or less, or 3.5% by weight or less. The lower limit may be 0.3% by weight or more, 0.5% by weight or more, 1.0% by weight or more, or 1.5% by weight or more. These comonomer content rates may apply whether the comonomer is a single molecule or multiple molecules. When the comonomer is ethylene, its content may be greater than 0% by weight and 7.0% by weight or less. When the comonomer is ethylene, the upper limit of its content may be 5.0% by weight or less, 4.0% by weight or less, or 3.5% by weight or less. The lower limit may be 0.3% by weight or more, 0.5% by weight or more, 1.0% by weight or more, or 1.5% by weight or more. The comonomer content in copolymer (A) can generally be determined by NMR measurement. The comonomer content can also be controlled by adjusting the amount of comonomer supplied during the manufacturing process of copolymer (A).

[0018] The method for calculating the comonomer content is: 13 Alternatively, one can use the following method, which involves determining the signal intensity of the 1C-NMR spectrum using the following formula. Propylene content (mol %) = I(C3) × 100 / (I(C3) + I(C2) + I(C4)) Ethylene content (mol %) = I(C2) × 100 / (I(C3) + I(C2) + I(C4)) 1-Butene content (mol%) = I(C4) × 100 / (I(C3) + I(C2) + I(C4)) In the above, I(C3) represents the integrated signal intensity based on propylene bonding, I(C2) represents the integrated signal intensity based on ethylene bonding, and I(C4) represents the integrated signal intensity based on butene bonding.

[0019] The integral intensities of each monomer and comonomer are determined as follows. I(C3) = I 49.0~44.4 + (I C + I C’ + I E + I G + I D ) / 5 + (I H + I I ) / 4 + (I O + I N ) + I L / 2 I(C2) = (I 25.0~24.0 + I 30.0~29.8 + I O + I N ) / 2 + (I 38.2~37.2 - I L + 3 × I 27.3~27.1 + I 30.5.~30.2 - (I C + I C’ + I E + I G + I D ) / 5 - I 39.71~39.61 + I H + I I ) / 4 I(C4) = I 41.00~39.00 + I 43.90~42.30 / 2 [[ID=*65]]Here, I C 、I C’ 、I E 、I G 、I D 、I H + I I 、I O + I N and I L mean the following. Ic: Signal area resonating around 17.1 ppm I C’ : Signal area resonating around 17.5 ppm I E : Signal area resonating around 35.7 ppm I G : Signal area resonating around 35.8 ppm I D : Signal area resonating around 42.1 ppm I O + I N : Signal area resonating around 34.9 ppm I *Note: There seems to be an error in the original text where "Here, I" is written as "ここで、I" in Japanese. I've translated it as "Here, I" in English while keeping the overall context intact. If this is not what you intended, please clarify the specific issue or the expected translation style for that part.*L Resonant signal area around 27.6 ppm I H +I I Resonant signal area around 34.7-34.5 ppm Note that I represents the integrated intensity, and the numerical subscript to I indicates the range of the chemical shift. For example, I 39.71~39.61 This shows the integrated intensity of the signal detected between 39.71 ppm and 39.61 ppm.

[0020] In addition to the above, the comonomer content is 13 The results of the 1C-NMR measurement can also be used to calculate the values ​​using (Equation-1), (Equation-2), (Equation-3), (Equation-4), (Equation-6), (Equation-7), and (Equation-13) disclosed in Japanese Patent No. 6863174. Furthermore, the values ​​can also be calculated according to J.Appl.Polym.Sci.80,2001,1880-1890.

[0021] The conversion of comonomer content from mol% to weight% is performed using the following formula. When there is only one type of comonomer: Comonomer content (weight %) = (MW × X / 100) / {MW × X / 100 + 42 × (1 - X / 100)} × 100 (Here, MW represents the molecular weight of the comonomer, and X represents the comonomer content in mole percent.) When there are two types of comonomers (comonomer 1 and comonomer 2): Comonomer 1 content (wt%)=(MW1×X1 / 100) / {MW1×X1 / 100+MW2×X2 / 100+42×(1-(X1+X2)) / 100)}×100 Comonomer 2 content (wt%)=(MW2×X2 / 100) / {MW1×X1 / 100+MW2×X2 / 100+42×(1-(X1+X2)) / 100)}×100 When multiple comonomers are present, the molecular weight of each comonomer is used in a general calculation.

[0022] <Characteristics (Ai): Melting peak temperature> The melting peak temperature (Tm) of copolymer (A), measured by DSC (differential scanning calorimetry), is in the range of 110°C to 150°C, preferably 115°C to 148°C, more preferably 120°C to 145°C, and even more preferably 120°C to 140°C. A Tm of 110°C or higher allows the copolymer (A) to possess high rigidity. Furthermore, a Tm of 150°C or lower ensures high quality in the fabricated object without compromising tactile properties or impact strength. In this specification, Tm is determined by the method described in the Examples section below.

[0023] <Characteristics (A-ii): Heat of fusion> The heat of fusion (ΔH) of copolymer (A), measured by DSC, is in the range of 80 J / g or less, more preferably 75 J / g or less. A heat of fusion ΔH of 80 J / g or less suppresses shrinkage due to the decrease in the temperature of the molten resin during molding, thus enabling the production of molded objects with a good appearance. There is no particular lower limit to the heat of fusion, but it is usually 40 J / g or higher. The method for measuring the heat of fusion is determined in the same way as for measuring the peak melting temperature.

[0024] <Characteristics (A-iii): MFR> The MFR (Mold Free Filtration Rate) of copolymer (A) at 230°C with a 2.16 kg load is in the range of 0.1 g / 10 min to 15 g / 10 min, preferably 0.2 g / 10 min to 13 g / 10 min, and more preferably 0.3 g / 10 min to 10 g / 10 min. When the MFR is 0.1 g / 10 min or higher, shrinkage is reduced in the resin composition for 3D modeling and the molded object, and the extruded resin is less prone to fluctuation during lamination, which is thought to improve moldability (shape accuracy and appearance). When the MFR is 15 g / 10 min or lower, excessive flow of the filler in the molten resin is suppressed, which is thought to have less impact on the outer surface of the molded object, and the appearance properties other than warping and deformation are improved while maintaining the adhesion between the laminated resins of the molded object. The MFR can also be adjusted by using a molecular weight lowering agent. In this specification, MFR is the value measured in accordance with JIS K7210 (2014) at a test temperature of 230°C and a load of 2.16 kg.

[0025] <Method for producing copolymer (A)> The method for producing copolymer (A) is not particularly limited and can be produced using, for example, a metallocene catalyst or a Ziegler catalyst.

[0026] (i) Metallocene catalyst The metallocene catalyst is not particularly limited as long as it can produce copolymer (A), but in order to satisfy the requirements of the present invention, for example, a metallocene catalyst consisting of components (a), (b), and component (c) as shown below may be used. Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1). Component (b): At least one solid component selected from (b-1) to (b-4) below. (b-1): Particulate carrier on which an organoaluminum oxy compound is supported. (b-2): A particulate carrier on which an ionic compound or Lewis acid capable of reacting with component (a) to convert component (a) into a cation is supported. (b-3): Solid acid fine particles (b-4): Ion-exchange layered silicate Ingredient (c): Organoaluminum compound

[0027] As component (a), at least one metallocene transition metal compound selected from the transition metal compounds represented by the following general formula (1) can be used. Q(C5H 4-a R 1 a )(C5H 4-b R 2 b )MeXY (1)

[0028] Q represents a divalent bonding group that bridges two conjugated five-membered ring ligands. Examples include a divalent hydrocarbon group, a silylene group or oligosilylene group, a silylene group or oligosilylene group having a hydrocarbon group as a substituent, or a germylene group having a hydrocarbon group as a substituent. Among these, the preferred are a divalent hydrocarbon group and a silylene group having a hydrocarbon group as a substituent. X and Y independently represent a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group. Preferred examples include hydrogen, chlorine, methyl, isobutyl, phenyl, dimethylamide, and diethylamide groups. X and Y may be the same or different from each other. R 1 and R 2 Each of these independently represents a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. Specific examples of hydrocarbon groups include methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl, naphthyl, butenyl, and butadienyl groups. Typical examples of halogenated hydrocarbon groups, silicon-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups, oxygen-containing hydrocarbon groups, boron-containing hydrocarbon groups, or phosphorus-containing hydrocarbon groups include methoxy, ethoxy, phenoxy, trimethylsilyl, diethylamino, diphenylamino, pyrazolyl, indolyl, dimethylphosphono, diphenylphosphono, diphenylboron, and dimethoxyboron groups. Among these, it is preferable that the hydrocarbon group has 1 to 20 carbon atoms, and particularly preferable that it be a methyl, ethyl, propyl, or butyl group. Here, adjacent R 1 and R 2 These groups may be bonded to each other to form a ring, and this ring may have substituents consisting of a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. a and b are substituents R, respectively. 1 and R2 This is a number, representing an integer between 0 and 4. Me is a metal atom selected from titanium, zirconium, and hafnium, and is preferably zirconium or hafnium.

[0029] Among component (a), those preferred for the production of copolymer (A) are transition metal compounds comprising ligands having hydrocarbon substituents on silylene groups, germylene groups, or alkylene groups, substituted cyclopentadienyl groups, substituted indenyl groups, substituted fluorenyl groups, or substituted azlenyl groups. Particularly preferred are transition metal compounds comprising ligands having hydrocarbon substituents on silylene groups, or 2,4-substituted indenyl groups or 2,4-substituted azlenyl groups, which are crosslinked with germylene groups.

[0030] Non-limiting specific examples of component (a) include dimethylsilylenebis(2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylenebis(2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis(2-methylbenzoindenyl) zirconium dichloride, dimethylsilylenebis{2-isopropyl-4-(3,5-diisopropylphenyl)indenyl} zirconium dichloride, dimethylsilylenebis(2-propyl-4-phenanthrylindenyl) zirconium dichloride, and dimethylsilylenebis(2-methyl-4-phenyl Examples include azlenyl) zirconium dichloride, dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)azlenyl} zirconium dichloride, dimethylsilylenebis(2-ethyl-4-phenylazlenyl) zirconium dichloride, dimethylsilylenebis(2-isopropyl-4-phenylazlenyl) zirconium dichloride, dimethylsilylenebis{2-ethyl-4-(2-fluorobiphenyl)azlenyl} zirconium dichloride, and dimethylsilylenebis{2-ethyl-4-(4-t-butyl-3-chlorophenyl)azlenyl} zirconium dichloride. Compounds obtained by replacing the silylene group with a germylene group and zirconium with hafnium in these specific examples are also exemplified as suitable compounds. Since the catalyst component is not an essential element of the present invention, a lengthy list has been avoided and only representative examples have been provided; however, it is self-evident that this does not limit the effective scope of the present invention.

[0031] As component (b), at least one solid component selected from components (b-1) to (b-4) is used. Each of these components is known and can be appropriately selected and used from known technologies. Detailed examples of specific components and manufacturing methods can be found in Japanese Patent Publication Nos. 2002-284808, 2002-53609, 2002-69116, and 2003-105015. Among the above components (b), particularly preferred is the ion-exchangeable layered silicate of component (b-4), and more preferably, the ion-exchangeable layered silicate subjected to chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic substance treatment.

[0032] Examples of the organoaluminum compound optionally used as component (c) include the following general formula (2): AlR a P 3-a (2) (In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, P represents hydrogen, a halogen, or an alkoxy group, and a represents a number where 0 < a ≤ 3.) Trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum, or halogen- or alkoxy-containing alkylaluminums such as diethylaluminum monochloride and diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Among these, trialkylaluminum is particularly preferred.

[0033] As a method for forming the catalyst, the above components (a), (b), and optionally component (c) are brought into contact to form a catalyst. The contact method is not particularly limited as long as it can form a catalyst, and known methods can be used.

[0034] Also, the usage amounts of components (a), (b), and (c) are arbitrary. For example, the usage amount of component (a) relative to 1 g of component (b) may be 0.1 μmol to 1,000 μmol, or may be 0.5 μmol to 500 μmol. The usage amount of component (c) relative to 1 g of component (b) may be 0.001 μmol to 100 mmol, or may be 0.005 μmol to 50 mmol. Furthermore, the catalyst used in the present invention is preferably subjected to a prepolymerization treatment which consists of preliminarily contacting with an olefin and performing a small amount of polymerization.

[0035] The metallocene catalyst-derived copolymer (A) can be a commercially available product; for example, the Wintec® series manufactured by Nippon Polypropylene Co., Ltd. is preferably used.

[0036] (ii) Ziegler catalyst Copolymer (A) can also be produced using a Ziegler catalyst. Examples of Ziegler catalysts include titanium trichloride or a titanium trichloride composition obtained by reducing titanium tetrachloride with organoaluminum, etc., and then further activated by treating it with an electron-donating compound (see, for example, Japanese Patent Publication Nos. 47-34478, 58-23806, and 63-146906), or a titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating it with various electron donors and electron acceptors, and an organoaluminum compound and an aromatic carboxylic acid. Examples include catalysts consisting of tere (see Japanese Patent Publication Nos. 56-100806, 56-120712, and 58-104907), and supported catalysts consisting of magnesium halide, titanium tetrachloride, and various electron donors (see Japanese Patent Publication Nos. 57-63310, 58-157808, 58-83006, 58-5310, 61-218606, 63-43915, and 63-83116).

[0037] The copolymer (A) derived from the Ziegler catalyst can be a commercially available product; for example, the Novatec® series manufactured by Nippon Polypropylene Co., Ltd. is preferably used.

[0038] (iii) Polymerization process For the time-dependent operation of the polymerization process, both batch and continuous methods can be used, but generally, continuous methods are preferable from a productivity standpoint. Possible polymerization methods include slurry polymerization using inert hydrocarbons such as hexane, heptane, octane, benzene, or toluene as the polymerization solvent; bulk polymerization using propylene itself as the polymerization solvent; and gas-phase polymerization in which the raw material propylene is polymerized in the gas phase. It is also possible to combine these polymerization methods.

[0039] The polymerization temperature can be set within the commonly used temperature range without any particular problems. Specifically, a range of 0°C to 200°C, more preferably 40°C to 100°C, can be used. The optimal polymerization pressure varies depending on the selected process, but any pressure within the commonly used range can be adopted without particular problems. Specifically, a relative pressure greater than 0 MPa and up to 200 MPa, more preferably in the range of 0.1 MPa to 50 MPa, can be used. In this case, an inert gas such as nitrogen may be present. Furthermore, when hydrogen is used as a molecular weight modifier, the molar ratio to propylene should be 1.0 × 10⁻⁶. -6 The above is 1.0 × 10 -2 It can be used within the following range: Preferably, 1.0 × 10 -5 The above is 0.9 × 10 -2 The following applies:

[0040] <Amount of copolymer (A)> The amount of copolymer (A) is 40% to 99% by weight, preferably 45% to 98% by weight, more preferably 50% to 95% by weight, and particularly preferably 55% to 90% by weight, based on 100% by weight of the total amount of copolymer (A) and filler (B). It is believed that if the amount of copolymer (A) is 40% by weight or more, the low shrinkage, scratch resistance, impact strength, and moldability of the 3D molding resin composition and the molded object can be sufficiently improved. On the other hand, if it is 99% by weight or less, rigidity can be maintained, which is believed to lead to an improvement in the strength of the molded object.

[0041] 2. Filler (B) Filler (B) can be any type of filler commonly used for resins. Recycled resin fillers can also be used. Specific examples of filler (B) include fibrous inorganic fillers such as glass fibers, carbon fibers, silicon carbide fibers, potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, alumina fibers, ceramic fibers, gypsum fibers, and metal fibers; non-fibrous inorganic fillers such as silica, talc, mica, clay, warlastenite, zeolite, sericite, kaolin, pyrophyllite, bentonite, montmorillonite, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, calcined kaolin, ceramic beads, boron nitride, and silicon carbide, or their calcined products; and organic fillers such as wood flour, cellulose powder, and cellulose fibers. Two or more of these may be used in combination as fillers. It is preferable to use at least one of the following as filler (B): talc, calcium carbonate, calcined kaolin, glass fiber, wood powder, cellulose powder, carbon fiber, and cellulose fiber; glass fiber is more preferable.

[0042] Furthermore, the filler (B) can also be used in the form of a so-called masterbatch, which is pre-mixed into the resin at a relatively high concentration. In addition to copolymer (A), other resins that can be used in the masterbatch (matrix resin) include, for example, polyethylene resins such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene wax, polypropylene (PP) resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-ethylene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin, polyamide (PA, nylon) resin, thermoplastic polyimide resin, thermoplastic urethane resin, and poly Examples include aminobismaleimide resin, polyamideimide resin, polyetherimide resin, polymethyl methacrylate resin, polyvinyl acetate resin, polycarbonate resin, polyacetal resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene oxide resin, polyphenylene sulfide (PPS) resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyallylsulfone resin, bismaleimide triazine resin, polymethylpentene resin, fluorine resin, liquid crystal polymer, olefin-vinyl alcohol copolymer, ionomer resin, polyarylate resin, etc. At least one of these can be used depending on the purpose.

[0043] Among the resins mentioned above, if at least one selected from the group consisting of polyethylene resins such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene wax, and polypropylene (PP) resin, which have excellent compatibility with copolymer (A), is used as the matrix resin, it is thought that the filler will be uniformly dispersed when fabricating a three-dimensional object, resulting in good shape accuracy by suppressing deformation of the three-dimensional object, especially warping, and improved adhesion between the laminated resins. For this reason, the matrix resin may also be copolymer (A).

[0044] When used as a masterbatch, the concentration of the filler in the masterbatch is not particularly limited, but may be 10-90% by weight, 20-80% by weight, or 50-70% by weight relative to 100% by weight of the entire masterbatch. Similarly, the matrix resin is not particularly limited, but may be 10-90% by weight, 20-80% by weight, or 30-50% by weight relative to 100% by weight of the entire masterbatch. If the filler concentration is 10% by weight or more, it is considered that good shape accuracy and the effect of maintaining interlayer resin adhesion can be obtained by suppressing deformation of the 3D molded object, especially warping. If the filler concentration is 90% by weight or less, it is considered advantageous in uniformly dispersing the filler when molding the 3D molded object, thereby suppressing appearance defects such as color unevenness and the occurrence of warping of the 3D molded object.

[0045] When the filler (B) is used in the form of a masterbatch and the matrix resin is a resin other than copolymer (A), the amount of matrix resin blended may be 0 to 150 parts by weight, 0.01 to 100 parts by weight, 0.5 to 50 parts by weight, or 1 to 20 parts by weight per 100 parts by weight of copolymer (A). If the blending amount is 150 parts by weight or less, it is considered that the shape accuracy of the 3D molding resin composition and the molded object, as well as the strength of the adhesive force between the laminated resins, will not decrease easily due to the suppression of warping, etc. The filler (B) that is particularly preferred will be described in detail below. Note that the filler (B) used in the form of a masterbatch may be one type or two or more types may be used in combination.

[0046] (i) Inorganic fillers (i-1) Glass fiber The glass fibers are not particularly limited and can be used. Examples of glass types used for the fibers include E glass, C glass, A glass, and S glass, with E glass being preferred. The manufacturing method for the glass fibers is not particularly limited and can be manufactured using various known manufacturing methods. Furthermore, glass fibers recovered from glass fiber reinforced plastics can be used. Specifically, examples include glass fibers recovered by methods disclosed in the Abstracts of Research Presentations at the 29th Autumn Meeting of the Society of Chemical Engineers, Japan, Vol. 3, p. 171, 1996, Japanese Patent Publication No. 2008-106183, Japanese Patent Publication No. 2011-184275, etc., but are not limited to these, and glass fibers recovered by known methods can be used. The fiber diameter of the glass fiber is preferably 3.0 μm to 25.0 μm, and more preferably 6.0 μm to 20.0 μm. If the fiber diameter is 3.0 μm or more, the glass fiber is less likely to break during the manufacturing of the 3D modeling resin composition and the molded object, and during the molding process. If the fiber diameter is 25.0 μm or less, it is believed that the effects of improving the low shrinkage, scratch resistance, rigidity, and impact strength of the 3D modeling resin composition and the molded object will be maintained. Furthermore, the fiber length of the glass fibers, depending on the type of glass fiber used, is more preferably 1.0 mm to 20.0 mm on average when measured with a digital microscope, and even more preferably 1.5 mm to 10.0 mm. An average fiber length of 1.0 mm or more is less likely to reduce the low shrinkage, rigidity, and impact strength of the resin composition for 3D modeling and the resulting molded object, while an average fiber length of 20.0 mm or less is less likely to reduce the tactile feel (smoothness) and uniformity of the laminated surface (variation in the thickness of the laminated resin) of the molded object. In this case, the fiber length refers to the length when glass fibers are used as raw materials. However, this does not apply to glass fiber-containing pellets, which are formed by melt-extruding a large number of continuous glass fibers together, as described later; in such cases, roving-like materials are usually used. Two or more types of glass fibers can also be used in combination.

[0047] Glass fibers can be used in both surface-treated and untreated forms, but it is preferable to use glass fibers that have been surface-treated with organic silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, silicone compounds, higher fatty acids, fatty acid metal salts, fatty acid esters, etc., in order to improve their dispersibility in polypropylene resins. Examples of organic silane coupling agents used in surface treatment include vinyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane. Examples of titanate coupling agents include isopropyltriisostearoyl titanate, isopropyltris(dioctyl pyrophosphate) titanate, and isopropyltri(N-aminoethyl) titanate. Examples of aluminate coupling agents include acetalkoxyaluminum diisopropylate. Examples of zirconate coupling agents include tetra(2,2-diallyloxymethyl)butyl, di(tridecyl)phosphytozirconate, neopentyl(diallyl)oxy, and trineodecanoylzirconate. Examples of the above silicone compounds include silicone oil and silicone resin.

[0048] Furthermore, examples of higher fatty acids used for surface treatment include oleic acid, capric acid, lauric acid, palmitic acid, stearic acid, montanic acid, caleic acid, linoleic acid, rosinic acid, linolenic acid, undecanoic acid, and undecenoic acid. Examples of higher fatty acid metal salts include fatty acids with 9 or more carbon atoms, such as sodium salts, lithium salts, calcium salts, magnesium salts, zinc salts, and aluminum salts of stearic acid and montanic acid. Among these, calcium stearate, aluminum stearate, calcium montanate, and sodium montanate are preferred. Examples of fatty acid esters include polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, alpha-sulfone fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyethylene fatty acid esters, and sucrose fatty acid esters. The amount of the above surface treatment agent used is not particularly limited, but may be 0.01 to 5 parts by weight, or 0.1 to 3 parts by weight, per 100 parts by weight of glass fiber.

[0049] Furthermore, the glass fibers may be those that have been treated (surface-treated) with a sizing agent. Examples of sizing agents include epoxy sizing agents, aromatic urethane sizing agents, aliphatic urethane sizing agents, acrylic sizing agents, and maleic anhydride-modified polyolefin sizing agents. These sizing agents need to melt during the melt-mixing process with polypropylene resins, and therefore may melt at temperatures below 200°C.

[0050] The glass fibers can also be used as so-called chopped strand glass fibers, which are obtained by cutting fiber filaments to a desired length. It is preferable to use these chopped strand glass fibers in order to further enhance the low shrinkage, rigidity, and impact strength effects of the resin composition for 3D modeling and the molded objects thereof.

[0051] Furthermore, these glass fibers may be used as "glass fiber-containing pellets" which are formed by melt-extruding a large number of continuous glass fibers together in a masterbatch using copolymer (A) or the above-mentioned resin in any amount, and in which the length of the glass fibers in the pellet is substantially the same as the length of one side (extrusion direction) of the pellet. This is more preferable because it further enhances the physical properties of the resin composition for 3D molding and the molded object, such as low shrinkage, scratch resistance, rigidity, and impact strength. In this case, "substantially" specifically means that, based on the total number of glass fibers in the glass fiber-containing pellet, 50% or more, preferably 90% or more, have a length that is the same as the length (extrusion direction) of the glass fiber-containing pellet, and that there is almost no fiber breakage during the preparation of the pellet. The method for manufacturing these glass fiber-containing pellets is not particularly limited, but for example, one method involves using a resin extruder to draw a large number of continuous glass fibers from a fiber rack through a crosshead die, and then melt-extruding (impregnating) them with an arbitrary amount of copolymer (A) in a molten state to assemble and integrate the large number of glass fibers (pulling method). Since there is almost no breakage of the fibers, the method for manufacturing glass fiber-containing pellets may also be the pulling method.

[0052] The length (extrusion direction) of the glass fibers contained in the glass fiber-containing pellets is preferably 1.0 mm to 20.0 mm, more preferably 1.5 mm to 15.0 mm, and even more preferably 2.0 mm to 10.0 mm, depending on the glass fibers used. If the length is 1.0 mm or more, it is less likely to reduce the physical properties of the 3D molding resin composition and the molded object, such as low shrinkage, scratch resistance, rigidity, and impact strength. If the length is 20.0 mm or less, it is less likely to reduce the tactile feel (smoothness) of the molded object and the uniformity of the laminated surface (variation in the thickness of the laminated resin). The method for determining the length of the fibers contained in glass fiber-containing pellets is not particularly limited. It may be the same as the method for determining the average length of glass fibers present in the resin composition for 3D modeling described later.

[0053] Furthermore, in the glass fiber-containing pellets, the glass fiber content is preferably 10% to 70% by weight, more preferably 20% to 60% by weight, and even more preferably 30% to 50% by weight, based on 100% by weight of the entire pellet. When glass fiber-containing pellets with a glass fiber content of 10% by weight or more are used, three-dimensional molded objects with excellent shape accuracy and rigidity can be obtained. When using pellets with a glass fiber content of 70% by weight or less, classification of pellets due to differences in specific gravity is less likely to occur when uniformly blended with copolymer (A) for three-dimensional molding, which is preferable for obtaining three-dimensional molded objects with uniform color and rigidity without uneven filler concentration.

[0054] (i-2) Carbon fiber The carbon fibers are not particularly limited in size or type, and can include extremely fine carbon fibers, such as those with a fiber diameter of 500.0 nm or less, also known as micro-carbon fibers. However, the fiber diameter may be between 2.0 μm and 20.0 μm, or between 3.0 μm and 15.0 μm. If the fiber diameter is 2.0 μm or larger, the carbon fibers are less likely to break during the manufacturing and molding of the 3D printing resin composition and its molded objects, and the effects of improving the physical properties such as low shrinkage, scratch resistance, rigidity, and impact strength of the 3D printing resin composition and its molded objects are less likely to decrease. Furthermore, if the fiber diameter is 20.0 μm or less, it is considered that the effects of improving the low shrinkage, scratch resistance, rigidity, and impact strength of the resin composition for 3D printing and the printed objects thereof will not decrease significantly. Here, the method for measuring the fiber diameter is a known method, such as JIS R7607 (formerly JIS R7601) or microscopic observation. Furthermore, the fiber length of the carbon fiber may be 1.0 mm to 20.0 mm, or 3.0 mm to 10.0 mm. In this case, fiber length refers to the length when carbon fibers are used directly as raw materials. However, this does not apply to "carbon fiber-containing pellets," which are formed by melt-extruding a large number of continuous carbon fibers and then assembling them into a single unit; in such cases, roving-like materials are usually used. If the fiber length is 1.0 mm or more, the final fiber length after manufacturing or molding of the 3D modeling resin composition and the molded object will not become too short, and the physical properties such as low shrinkage, rigidity, and impact strength of the 3D modeling resin composition and the molded object will not decrease. If the fiber length is 20.0 mm or less, it is considered that the tactile feel (smoothness) and uniformity of the layered surface (variation in the thickness of the layered resin) of the molded object will not decrease. In addition, two or more types of carbon fibers can be used in combination.

[0055] As mentioned above, there are no particular limitations on the type of carbon fiber, but examples include PAN (polyacrylonitrile) carbon fiber made primarily from acrylonitrile, pitch carbon fiber made primarily from tar pitch, and rayon carbon fiber, all of which can be suitably used. All of these fibers are highly suitable for the present invention, but PAN carbon fiber is preferred from the viewpoint of compositional purity and uniformity. These may be used individually or in combination. The manufacturing method of these carbon fibers is not particularly limited. Specific examples of carbon fiber include PAN-based carbon fiber such as "Pyrophil" manufactured by Mitsubishi Rayon, "Torayca" manufactured by Toray Industries, and "Besfight" manufactured by Toho Tenax, and pitch-based carbon fiber such as "Diaread" manufactured by Mitsubishi Plastics, "Donacarbo" manufactured by Osaka Gas Chemical Co., Ltd., and "Crecca" manufactured by Kureha Chemical Co., Ltd. Furthermore, carbon fibers recovered from carbon fiber reinforced plastics can be used. Specifically, examples include carbon fibers recovered by methods disclosed in Japanese Patent Publication No. 7-33904, Japanese Patent Publication No. 2013-64219, Japanese Patent Publication No. 2017-2125, and Japanese Patent Publication No. 2019-136932, but are not limited to these, and carbon fibers recovered by known methods can be used.

[0056] Carbon fibers typically have a tensile modulus of about 200 GPa to 1000 GPa. However, in this invention, considering the strength and economic efficiency of the resin composition for 3D modeling and the resulting molded object, carbon fibers with a modulus of 200 GPa to 900 GPa may be used, or even 200 GPa to 300 GPa may be used. Furthermore, carbon fiber typically has a density of 1.7 g / cm³. 3 ~5.0g / cm 3 It has a certain density, but due to its light weight and cost-effectiveness, it is 1.7 g / cm³. 3 ~2.5g / cm 3 You may also use materials having a certain density. Here, the methods for measuring the tensile modulus and density are known methods, for example, JIS R7606 can be cited for measuring the tensile modulus, and similarly, JIS R7603 can be cited for measuring the density.

[0057] These carbon fibers can be used as so-called chopped (strand-shaped) carbon fibers (hereinafter simply referred to as CCF), which are obtained by cutting fiber filaments to a desired length, or they may be bundled using various sizing agents as needed. These CCFs may be used to further enhance the effects of improving various physical properties such as low shrinkage, scratch resistance, rigidity, and impact strength in resin compositions for 3D modeling and the molded objects thereof. Specific examples of such CCF include, in the case of PAN-based carbon fiber, "Pyrophil Chop" manufactured by Mitsubishi Rayon, "Torayca Chop" manufactured by Toray Industries, and "Besfight Chop" manufactured by Toho Tenax, and in the case of pitch-based carbon fiber, "Diareed Chopped Fiber" manufactured by Mitsubishi Plastics, "Donacarbo Chop" manufactured by Osaka Gas Chemical Co., Ltd., and "Kureka Chop" manufactured by Kureha Chemical Co., Ltd.

[0058] Furthermore, these carbon fibers may be used as "carbon fiber-containing pellets" which are formed by melt-extruding them with a copolymer (A) or the above-mentioned resin in any amount to form a pellet containing a large number of continuous carbon fibers, and in which the length of the carbon fibers in the pellet is substantially the same as the length of one side (extrusion direction) of the pellet. This is because it enhances the properties of the resin composition for 3D modeling and the molded objects thereof, such as low shrinkage, rigidity, and impact strength. In this case, "substantially" specifically means that, based on the total number of carbon fibers in the carbon fiber-containing pellet, 50% or more, preferably 90% or more, have a length that is the same as the length (extrusion direction) of the carbon fiber-containing pellet, and that there is almost no fiber breakage during the preparation of the pellet. The method for manufacturing these carbon fiber-containing pellets is not particularly limited, but one example is a method (pultrusion method) in which a large number of continuous carbon fibers are drawn from a fiber rack through a crosshead die using a resin extruder, and then melt-extruded (impregnated) with an arbitrary amount of copolymer (A) in a molten state to assemble and integrate the large number of carbon fibers. Since there is almost no breakage of the fibers, the method for manufacturing carbon fiber-containing pellets may also be the pultrusion method.

[0059] The length (extrusion direction) of the carbon fiber-containing pellets may be between 1.0 mm and 20.0 mm, depending on the carbon fiber used. If the length is 1.0 mm or longer, it is less likely to reduce the physical properties of the 3D modeling resin composition and the modeled object, such as low shrinkage, scratch resistance, rigidity, and impact strength. If the length is 20.0 mm or less, it is less likely to reduce the tactile feel (smoothness) of the modeled object and the uniformity of the layered surface (variation in the thickness of the layered resin). Furthermore, in the carbon fiber-containing pellets, the carbon fiber content is preferably 10% to 70% by weight relative to 100% by weight of the entire pellet. When carbon fiber-containing pellets with a carbon fiber content of 10% by weight or more are used, three-dimensional molded objects with excellent shape accuracy and rigidity can be obtained. When using pellets with a carbon fiber content of 70% by weight or less, classification of pellets due to differences in specific gravity is less likely to occur when uniformly blended with resin A for three-dimensional molding, which is preferable for obtaining three-dimensional molded objects with uniform color and rigidity without uneven filler concentration.

[0060] (i-3) Whisker While there are no particular limitations on the type of whisker that can be used, specific examples include basic magnesium sulfate fibers (magnesium oxysulfate fibers), potassium titanate fibers, aluminum borate fibers, calcium silicate fibers, and calcium carbonate fibers. Among these, basic magnesium sulfate fibers (magnesium oxysulfate fibers), potassium titanate fibers, and calcium carbonate fibers are preferred, with basic magnesium sulfate fibers (magnesium oxysulfate fibers) being particularly preferred. The fiber diameter of the whisker is not particularly limited, but may be 1.0 μm or less. Similarly, the fiber length is not particularly limited, but may be between 0.1 μm and 100.0 μm, between 0.5 μm and 50.0 μm, or between 1.0 μm and 20.0 μm. If the fiber diameter is 1 μm or larger, it is considered that the resin composition for 3D modeling and the resulting molded objects are less likely to experience a decrease in low shrinkage, scratch resistance, and rigidity / impact strength. Methods for measuring fiber diameter are known, such as microscopic observation. Furthermore, two or more types of whiskers can be used in combination.

[0061] Whiskers are not particularly limited in their manufacturing method and can be produced using various known methods. For example, basic magnesium sulfate fibers are produced by methods such as hydrothermal synthesis using magnesium hydroxide and magnesium sulfate as raw materials. Furthermore, while whiskers are generally in the form of a fine powder, they may also be used in the form of compressed lumps, granules, or granulated materials, manufactured to improve mixing efficiency. These whiskers may also be surface-treated with various surface treatment agents, such as organic titanate coupling agents, organic silane coupling agents, unsaturated carboxylic acids, or modified polyolefins grafted with their anhydrides, fatty acids, fatty acid metal salts, and fatty acid esters, for purposes such as improving adhesion or dispersibility with copolymers (A).

[0062] (i-4) Other inorganic fillers Non-fibrous inorganic compounds can also be used. Preferably, such fillers contain silicon dioxide as the main component, and specific examples include talc, mica, clay, montmorillonite, and bentonite. Among these, talc is preferred from the viewpoint of strength in the layering direction of the three-dimensional object and the accuracy of the molding process. These inorganic fillers may be used individually or in combination of two or more types.

[0063] Talc is a layered mineral sometimes called talc, French chalk, steatite, or soapstone. Its chemical formula varies depending on the source, but for example, Mg3Si4O 10 It is represented as (OH)2. In this invention, commercially available talc can be selected as the filler material.

[0064] The particle size of talc is not particularly limited and can be selected according to the purpose, but from the viewpoint of uniformly mixing it into the resin composition for 3D molding, an average diameter of 1.0 μm to 100.0 μm is preferred, 2.0 μm to 20.0 μm is more preferred, 3.0 μm to 13.0 μm is even more preferred, and 3.0 μm to 6.0 μm is particularly preferred. When the average diameter falls within the above range, it is believed that a 3D molded object with excellent inter-layer resin adhesion strength and good shape accuracy with suppressed warping and other issues can be obtained. The talc particle size mentioned above is the median diameter (D50) (μm) value measured using a laser diffraction scattering particle size analyzer or similar device. A specific measuring device is, for example, the LA-920 model manufactured by Horiba, Ltd. Alternatively, one can refer to a catalog of commercially available products, and measurement can also be performed using analytical methods in accordance with the standards of the Ceramic Society of Japan.

[0065] (ii) Organic fillers As organic fillers, known organic compounds used as resin fillers, such as organic fibers like cellulose fibers and aramid fibers, wood flour, and cellulose powder, can be used. In particular, organic fibers with a melting point of 245°C or higher can be used. As long as the melting point is 245°C or higher, the type and dimensions of the organic fiber are not particularly limited. Specifically, examples include polyester fibers, polyamide fibers, polyphenylene sulfide fibers, and aramid fibers, with polyester fibers and polyamide fibers being particularly suitable. Examples of polyester fibers include polyethylene terephthalate (PET) fibers and polyethylene naphthalate (PEN) fibers, and examples of polyamide fibers include polyamide 66 fibers. The melting point is defined as the melting peak temperature of the DSC curve in accordance with JIS K7121. Two or more types of organic fibers may be used in combination, and furthermore, natural fibers such as cotton may be included in less than 50% by weight of the total 100% by weight of the organic fibers (e.g., cotton blends). Furthermore, the method for producing the organic fibers is not particularly limited and can be produced by various known manufacturing methods.

[0066] The single filament fineness of these organic fibers and organic compounds used as resin fillers (hereinafter sometimes referred to as "organic fibers, etc.") is usually 1 dtex to 20 dtex, and may also be 2 dtex to 15 dtex. Furthermore, the total fineness of the organic fibers, etc. is usually 150 dtex to 3,000 dtex, and may also be 250 dtex to 2,000 dtex. In addition, the number of filaments of the organic fibers, etc. is usually 10 filaments to 1,000 filaments, and may also be 50 filaments to 500 filaments. Furthermore, the fiber length may range from 1.0 mm to 20.0 mm, depending on the type of organic fiber used. A fiber length of 1.0 mm or more is less likely to reduce the physical properties of the 3D modeling resin composition and the resulting model, such as low shrinkage, scratch resistance, rigidity, and impact strength. A fiber length of 20.0 mm or less is less likely to reduce the tactile feel (smoothness) of the model and the uniformity of the laminated surface (variation in the thickness of the laminated resin). In this case, the fiber length refers to the length when organic fibers are used as raw materials. However, this does not apply to "fiber-containing pellets of organic fibers, etc.," which are formed by melt-extruding and assembling a large number of continuous fibers, as described later; in such cases, roving-like materials are usually used. Note that two or more types of organic fibers can be used in combination.

[0067] As described above, these organic fibers are melt-kneaded together with copolymer (A) to form a resin composition for 3D modeling. However, if the organic fibers are organic fibers such as cellulose fibers or aramid fibers, their melting point is 245°C or higher. Therefore, there is a significant difference in melting properties (melting point (softening point)) between them and copolymer (A), which has a lower melting point (softening point). For example, during melt-kneading, which is usually around 200°C, thermal deformation of the organic fibers is sufficiently suppressed, and the fibrous form (aspect ratio) of the organic fibers is sufficiently maintained. As a result, it is believed that the resin composition for 3D modeling and the molded objects produced therefrom exhibit good physical properties such as low shrinkage, scratch resistance, rigidity, and impact strength.

[0068] Furthermore, these organic fibers are melt-extruded in an arbitrary amount-to-amount ratio with copolymer (A) or the above-mentioned resin to form pellets in which a large number of continuous fibers are aggregated and integrated, and the length of the fibers in the pellets is substantially the same as the length of one side (extrusion direction) of the pellet. Using these as "fiber-containing pellets containing organic fibers" enhances the low shrinkage, scratch resistance, rigidity, and impact strength of the resin composition for 3D molding and the molded objects thereof. In this case, "substantially" means that, based on the total number of fibers in the fiber-containing pellets containing organic fibers, 50% or more, preferably 90% or more, have a length that is the same as the length of the fiber-containing pellets containing organic fibers, and that the fibers do not break during the preparation of the pellets. The method for producing these fiber-containing pellets, such as organic fibers, is not particularly limited. For example, one method involves using a resin extruder to draw a large number of continuous organic fibers from a fiber rack through a crosshead die, while melt-extruding (impregnating) an arbitrary amount of copolymer (A) in a molten state to assemble and integrate the large number of organic fibers (pulling method). Since these methods result in almost no fiber breakage, these methods are also acceptable.

[0069] The length of the fiber-containing pellets, such as organic fibers, is preferably between 1.0 mm and 20.0 mm, although this depends on the type of organic fiber used. A length of 1.0 mm or more is less likely to reduce the low shrinkage, scratch resistance, rigidity, and impact strength of the 3D modeling resin composition and the resulting modeled object. A length of 20.0 mm or less is less likely to reduce the tactile feel (smoothness) of the modeled object and the uniformity of the layered surface (variation in the thickness of the layered resin). Furthermore, in fiber-containing pellets such as organic fibers, the proportion of organic fibers is preferably 10 to 70% by weight relative to 100% by weight of the entire pellet. When using organic fiber-containing pellets with an organic fiber content of 10% by weight or more, three-dimensional molded objects with excellent shape accuracy and rigidity can be obtained. When using pellets with an organic fiber content of 70% by weight or less, when uniformly blended with copolymer (A) for three-dimensional molding, classification of pellets due to differences in specific gravity is less likely to occur, which is preferable for obtaining three-dimensional molded objects with uniform color and rigidity without uneven filler concentration.

[0070] (iii) Compounding amount The amount of filler (B) is 1% to 60% by weight, preferably 2% to 55% by weight, more preferably 5% to 50% by weight, and even more preferably 10% to 45% by weight, based on 100% by weight of the total amount of copolymer (A) and filler (B). If the amount of filler (B) is 1% by weight or more, it is considered that the properties of the 3D modeling resin composition and the modeled object, such as low shrinkage, scratch resistance, rigidity, and impact strength, will not deteriorate easily. On the other hand, if it is 60% by weight or less, it is considered that the tactile feel (smoothness) of the modeled object and the uniformity of the laminated surface (variation in the thickness of the laminated resin) will not deteriorate easily. Here, the amount of filler (B) is the actual amount; for example, when using the glass fiber-containing pellets mentioned above, it is calculated based on the actual content of glass fibers, which are the filler (B), contained in the pellets.

[0071] 3. Compatibilizer (C) The resin composition for 3D modeling contains a copolymer (A) and a filler (B), in addition to a compatibilizer (C). Examples of compatibilizers (C) include modified polyolefins, fatty acid amides, and other resins. One type of compatibilizer (C) or two or more types may be used in combination.

[0072] (i) Modified polyolefins The modified polyolefin is preferably at least one selected from acid-modified polyolefins and hydroxy-modified polyolefins. The modified polyolefin functions as a binder between the copolymer (A) and the filler (B), and has the characteristic of imparting higher levels of physical properties and functions such as low shrinkage, scratch resistance, smooth feel, rigidity, and impact strength to the resin composition for 3D molding and the molded object thereof. The acid-modified polyolefin is modified by graft copolymerizing polyolefins such as polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-α-olefin-non-conjugated diene compound copolymer (EPDM, etc.), and ethylene-aromatic monovinyl compound-conjugated diene compound copolymer rubber using an unsaturated carboxylic acid such as maleic acid or maleic anhydride. This graft copolymerization is carried out, for example, by reacting the above polyolefin with an unsaturated carboxylic acid in a suitable solvent using a radical generating agent such as benzoyl peroxide. In addition, the unsaturated carboxylic acid or its derivative component can also be introduced into the polymer chain by random or block copolymerization with a monomer for polyolefin.

[0073] Examples of unsaturated carboxylic acids used for modification include compounds having polymerizable double bonds into which carboxyl groups and, if necessary, functional groups such as hydroxyl groups or amino groups have been introduced, such as maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid. Derivatives of unsaturated carboxylic acids include their acid anhydrides, esters, amides, imides, and metal salts. Specific examples include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, acrylamide, methacrylamide, monoamide maleate, diamide maleate, monoamide fumarate, maleimide, N-butylmaleimide, and sodium methacrylate. Maleic anhydride is preferred.

[0074] Known conditions can be used for the graft reaction. For example, the method described in Japanese Patent Publication No. 2013-67789 can be employed.

[0075] The amount of acid modification (sometimes referred to as the graft rate) of the acid-modified polyolefin is not particularly limited, but preferably the amount of acid modification is 0.05 to 10% by weight, more preferably 0.07 to 5% by weight, in terms of maleic anhydride. A preferred acid-modified polyolefin is maleic anhydride-modified polypropylene, which has a significant effect in the present invention.

[0076] Hydroxyl-modified polyolefins are modified polyolefins that contain hydroxyl groups. These modified polyolefins may have hydroxyl groups at appropriate locations, such as the ends of the main chain or in side chains. Examples of olefin resins constituting hydroxy-modified polyolefins include α-olefins alone or copolymers such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene, and dodecene, as well as copolymers of the above α-olefins with copolymerizable monomers.

[0077] Preferred hydroxy-modified polyolefins include hydroxy-modified polyethylene (e.g., low-density, medium-density, or high-density polyethylene, linear low-density polyethylene, ultra-high molecular weight polyethylene, ethylene-(meth)acrylic acid ester copolymer, ethylene-vinyl acetate copolymer, etc.), hydroxy-modified polypropylene (e.g., polypropylene homopolymers such as isotactic polypropylene, random copolymers of propylene and α-olefins (e.g., ethylene, butene, hexane, etc.), propylene-α-olefin block copolymer, etc.), and hydroxy-modified poly(4-methylpentene-1). Examples of monomers for introducing the above-mentioned reactive groups include monomers having a hydroxyl group (e.g., allyl alcohol, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.). The amount of modification with monomers having hydroxyl groups is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, relative to 100% by weight of the hydroxy-modified polyolefin. The average molecular weight of the hydroxy-modified polyolefin is not particularly limited. In the case of low molecular weight systems, the hydroxy-modified polyolefin can be obtained by polymerizing conjugated diene monomers by known methods such as anionic polymerization, hydrolyzing the polymer, and then hydrogenating the resulting polymer.

[0078] (ii) Fatty acid amides As for fatty acid amides, the general formula is: R 4 CONH2[Here, R 4 Fatty acid amides, represented by [where represents a linear aliphatic hydrocarbon group having 10 to 25 carbon atoms], can be used. Fatty acid amides have the effect of reducing surface friction and other functions such as scratch resistance and abrasion resistance in resin compositions for 3D molding and the molded objects thereof, and reducing whitening marks. Examples of fatty acid amides include saturated fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide, and unsaturated fatty acid amides such as oleic acid amide, linoleic acid amide, linolenic acid amide, erucic acid amide, arachidonic acid amide, eicosapentaenoic acid amide, and docosahexaenoic acid amide. Among these, unsaturated fatty acid amides are also acceptable, and among them, monounsaturated fatty acid amides such as erucic acid amide and oleic acid amide may also be acceptable.

[0079] (iii) Other resins Other substances besides those listed in (i) and (ii) above that can be used as compatibilizers (C) include, for example, polyethylene resins, polypropylene resins (not copolymers (A)), polyvinyl chloride, polystyrene, polyvinylidene fluoride, and polyvinyl acetate. In addition, copolymers, graft resins, and blend resins mainly composed of polyolefin resins can be used, such as ethylene-vinyl chloride copolymers, vinyl acetate-ethylene copolymers, vinyl acetate-vinyl chloride copolymers, urethane-vinyl chloride copolymers, and acrylonitrile-butadiene-styrene copolymers. Of these resins, polyethylene resins and polypropylene resins (not copolymer (A)) are preferred from the viewpoint of further improving the balance of physical properties of the three-dimensional molding resin composition of the present invention, and polypropylene resins (not copolymer (A)) are particularly preferred. In addition, among polypropylene resins, at least one polypropylene resin selected from the group consisting of propylene homopolymers that do not fall under copolymer (A), propylene-α-olefin random copolymers, and propylene·α-olefin block copolymers is preferred.

[0080] The amount of compatibilizer (C) should be 0.1 parts by weight or more, preferably 0.5 parts by weight or more, more preferably 1.0 part by weight or more, and even more preferably 3.0 parts by weight or more, when the total weight of copolymer (A) and filler (B) is 100 parts by weight. There is no particular upper limit to the amount of compatibilizer (C) to be included, but it is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 50 parts by weight or less, when the total weight of copolymer (A) and filler (B) is 100 parts by weight. If the amount is 150 parts by weight or less, it is considered that the shape accuracy of the 3D molding resin composition and the molded object, as well as the strength of the adhesive force between the laminated resins, will not decrease easily.

[0081] 4. Other ingredients The resin composition for 3D modeling may contain other components in amounts that do not impair the effects of the present invention, in addition to the copolymer (A), filler (B), and compatibilizer (C). Examples of other components that can be used include thermoplastic elastomers and other resins, and additives commonly used in resins for 3D modeling, such as conventionally known antioxidants, light stabilizers, ultraviolet absorbers, neutralizing agents, lubricants, antistatic agents, metal deactivators, surfactants, colorants, pigments, crosslinking agents, foaming agents, nucleating agents, flame retardants, plasticizers, dispersants, antibacterial and antifungal agents, and conductive materials. The use of these additives is appropriately selected according to the application of the modeling. Each of these components may be added to the composition, or added individually to the copolymer (A), etc., and two or more of each component may be used in combination. The blending ratio of the additives can be adjusted according to the application of each additive.

[0082] As the thermoplastic elastomer, at least one selected from olefin-based elastomers (but not copolymer (A)) and styrene-based elastomers can be used. Using a thermoplastic elastomer is preferable because it can further impart functions such as low shrinkage, a soft feel, and high impact strength to the resin composition for three-dimensional molding and the molded object thereof. Examples of olefin-based elastomers include ethylene-α-olefin copolymer elastomers such as ethylene-propylene copolymer elastomer (EPR), ethylene-butene copolymer elastomer (EBR), ethylene-hexene copolymer elastomer (EHR), and ethylene-octene copolymer elastomer (EOR); and ethylene-α-olefin-diene terpolymer elastomers such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-butadiene copolymer, and ethylene-propylene-isoprene copolymer.

[0083] Examples of styrene-based elastomers include styrene-butadiene-styrene triblock copolymer elastomer (SBS), styrene-isoprene-styrene triblock copolymer elastomer (SIS), styrene-ethylene-butylene copolymer elastomer (SEB), styrene-ethylene-propylene copolymer elastomer (SEP), styrene-ethylene-butylene-styrene copolymer elastomer (SEBS), styrene-ethylene-butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene-butadiene elastomer (HSBR), styrene-ethylene-propylene-styrene copolymer elastomer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer elastomer (SEEPS), and styrene-butadiene-butylene-styrene copolymer elastomer (SBBS). Furthermore, hydrogenated polymer elastomers such as ethylene-ethylene-butylene-ethylene copolymer elastomer (CEBC) can also be mentioned. In particular, the use of ethylene-octene copolymer elastomer (EOR) and / or ethylene-butene copolymer elastomer (EBR) is preferred because it tends to result in superior performance in 3D molding resin compositions and their molded objects, such as lower shrinkage, better tactile feel, and greater impact strength, as well as greater cost-effectiveness. Two or more thermoplastic elastomers can also be used in combination.

[0084] The thermoplastic elastomer may include a propylene-based elastomer that does not fall under copolymer (A). Examples of such propylene-based elastomers include copolymers containing propylene and ethylene or olefins having 4 to 10 carbon atoms that do not satisfy at least one of the above characteristics (Ai) to (A-iii), as well as propylene-based block copolymers. Block copolymers can be obtained, for example, by step polymerization using a metallocene catalyst or a Ziegler catalyst.

[0085] The material may also contain resins other than the thermoplastic elastomers mentioned above. Examples include polyethylene resins, polypropylene resins (not copolymer (A)), polyvinyl chloride, polystyrene, polyvinylidene fluoride, and polyvinyl acetate. Furthermore, copolymers, graft resins, and blend resins mainly composed of the polyolefin resins mentioned above can be used, such as ethylene-vinyl chloride copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-vinyl chloride copolymer, urethane-vinyl chloride copolymer, and acrylonitrile-butadiene-styrene copolymer. Of these resins, polyethylene resins and polypropylene resins (not copolymer (A)) are preferred from the viewpoint of further improving the balance of physical properties of the three-dimensional molding resin composition of the present invention, and polypropylene resins (not copolymer (A)) are particularly preferred. In addition, among polypropylene resins, at least one polypropylene resin (not copolymer (A)) selected from the group consisting of propylene homopolymers, propylene-α-olefin random copolymers, and propylene·α-olefin block copolymers, which do not fall under the present invention, is also preferred.

[0086] As colorants, inorganic or organic pigments are effective in imparting and improving the colored appearance, aesthetics, texture, commercial value, weather resistance, and durability of polypropylene resin compositions and their molded articles. Examples of inorganic pigments include carbon black such as furnace carbon and Ketjencarbon; titanium dioxide; iron oxide (such as red iron oxide); chromic acid (such as yellow lead); molybdic acid; selenides sulfides; and ferrocyanides. Examples of organic pigments include azo pigments such as sparingly soluble azo lakes, soluble azo lakes, insoluble azo chelates, condensing azo chelates, and other azo chelates; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; surene pigments such as anthraquinone, perinone, perylene, and thioindigo; dye lakes; quinacridone-based pigments; dioxazine-based pigments; and isoindolinone-based pigments. In addition, aluminum flakes and pearl pigments can be included to create metallic or pearlescent finishes. Dyes can also be included.

[0087] For example, hindered amine compounds, benzotriazole compounds, benzophenone compounds, and salicylate compounds are effective as light stabilizers and ultraviolet absorbers in providing and improving the weather resistance and durability of polypropylene resin compositions and their molded articles, and are also effective in further improving weather resistance and discoloration. Specific examples of hindered amine compounds include the condensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine; poly[[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]]; 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-butanetetracarboxylate; bis(1,2,2,6,6-pentame Examples of light stabilizers include tyl-4-piperidyl sebacate and bis-2,2,6,6-tetramethyl-4-piperidyl sebacate. Benzotriazole-based materials include 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole. Benzophenone-based materials include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone. Salicylate-based materials include 4-t-butylphenyl salicylate and 2,4-di-t-butylphenyl 3',5'-di-t-butyl-4'-hydroxybenzoate. Using a light stabilizer and an ultraviolet absorber in combination is preferable because it greatly improves weather resistance, durability, and weather-induced discoloration resistance.

[0088] As antioxidants, for example, phenolic, phosphorus-based, and sulfur-based antioxidants are effective in imparting and improving the heat resistance, processing stability, and heat aging resistance of polypropylene resin compositions and their molded articles. Furthermore, as antistatic agents, for example, nonionic and cationic antistatic agents are effective in imparting and improving the antistatic properties of polypropylene resin compositions and their molded articles.

[0089] 5. Method for manufacturing resin compositions for 3D modeling A resin composition for three-dimensional molding can be obtained by kneading a copolymer (A), a filler (B), and a compatibilizer (C), along with additives as needed, by known means. The kneading method can be any method known to those skilled in the art, and is usually carried out using mixing equipment such as a tumbler, V-blender, ribbon blender, or super mixer. When melt kneading is performed, (semi-)melt kneading and granulation are usually carried out using kneading equipment such as a single-screw extruder, twin-screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader, super mixer (inverter / geration type), or agitator granulator. Furthermore, there are no particular restrictions on the method of adding each component. For example, the copolymer (A) and compatibilizer (C) may be kneaded in advance, and the filler (B) may be side-fed. Alternatively, the filler (B) may be top-fed together with the copolymer (A) and compatibilizer (C).

[0090] In the manufacture of resin compositions for 3D modeling, when the filler (B) present in the molten-mixed resin composition obtained through a molten-mixing process, or in its pellets, or in the molded object, is an inorganic fiber such as glass fiber or carbon fiber, or an organic fiber such as polyamide fiber or cellulose fiber, it is preferable to manufacture it by a composite method such that the average length of the filler (B) is 0.1 mm or more and 2.5 mm or less, more preferably 0.2 mm or more and 1.2 mm or less, and even more preferably 0.4 mm or more and 0.8 mm or less. An average length of 0.1 mm or more is preferable for obtaining a 3D molded object with excellent strength and good shape accuracy with suppressed warping, etc. An average length of 2.5 mm or less is preferable because it ensures stability of raw material supply to the 3D modeling equipment and stability of the thickness of the layered resin, and prevents problems with appearance and tactile properties other than deformation such as warping, such as fuzzing, during molding.

[0091] Here, the average length of the filler (B) present in the molten resin composition or its pellets, or in the molded object, refers to the value calculated as an average using values ​​measured with a digital microscope. The method of determination is not particularly limited, but a specific measurement method is, for example, when the filler (B) is glass fiber and carbon fiber, to remove the resin portion contained in the 3D molding resin composition or molded object by incineration in a high-temperature electric furnace, mix the resulting ashes of glass fiber and carbon fiber with surfactant-containing water, drop and diffuse the mixed solution onto a thin glass plate, and then measure the length of each fiber using a digital microscope (Keyence VHX-900 model) and calculate the average value.

[0092] Furthermore, a preferred manufacturing method is, for example, in melt kneading using a twin-screw extruder, in which, for example, a copolymer (A) and other components as needed are thoroughly melt-kneaded, and then a filler (B) is fed by a side-feed method or the like, to disperse the bundled fibers while minimizing fiber breakage. Furthermore, a so-called stirring granulation method, in which each component is supplied and stirred at high speed in a super mixer (inverter-type granulation) to a semi-molten state while the filler (B) in the mixture is kneaded, is also a preferred manufacturing method because it minimizes fiber breakage while easily dispersing the fibers. Furthermore, a manufacturing method in which each component except for the filler (B) is melted and kneaded in advance using an extruder or the like to form pellets, and then mixed with so-called "fiber-containing pellets" such as the glass fiber-containing pellets or carbon fiber-containing pellets to produce a resin composition for three-dimensional molding is also a preferred manufacturing method for the same reasons as described above. As described above, one possible method for manufacturing a resin composition for 3D modeling is to knead the components other than the filler (B) in the kneading process, and then add the filler (B). This method allows for the easy production of a resin composition for 3D modeling.

[0093] In the manufacture of resin compositions for 3D modeling, if the filler (B) present in the molten-mixed resin composition or its pellets obtained through a melt-mixing process, or in the modeled object, is a plate-shaped filler such as talc, mica, or montmorillonite, the average diameter of the filler (B) does not change significantly from that of the raw material and the molten-mixed resin composition or its pellets. Therefore, it may be the average diameter described above as the particle size of talc. The method for determining this average diameter is as described above.

[0094] The compounded resin or molten compounded resin composition can be used in pellet form, but may also be further processed into a filament. Filaments of resin compositions for 3D printing can be formed by any method known in the art. For example, pellets of the resin composition for 3D printing can be fed into an extruder, extruded through a die in a molten state at a temperature higher than the melting peak temperature of the copolymer, and then cooled to form a filament of a desired diameter. The filament can be obtained as a filament of any diameter depending on the diameter of the die used for extrusion, but the filament diameter may be in the range of 1.5 mm to 3.1 mm.

[0095] The resulting pellets or filaments can be used as a resin composition for 3D printing in their current state, but they may also be conditioned by further drying. "Conditioned" means that they have been treated under reduced pressure and heat for a certain period of time and are in a dried state. The conditions for conditioning are not particularly limited as long as the environment does not cause the filament to melt or deform, but examples include placing them under reduced pressure of 20 mm / Hg to 25 mm / Hg and in an environment of 55°C to 65°C for 24 hours or more. "Unconditioned" here means that the material has been stored at room temperature and pressure, and in particular, that it has been in that state for more than one week.

[0096] The resin composition for 3D printing can be used to manufacture articles by molten resin extrusion. This allows articles containing the resin composition for 3D printing to be fabricated using 3D printing technology. The method for manufacturing articles by 3D printing includes the step of depositing the resin composition for 3D printing in multiple layers using a 3D printer to form an article.

[0097] In the molten resin extrusion method, 3D printing can be performed using fused filaments. In this method, the filament containing the copolymer is supplied through a die heated to a sufficient temperature. The heating temperature is above the melting point of the copolymer and is not particularly limited as long as it is sufficient to melt the filament. By including the copolymer, the heating temperature can be kept relatively low. The molten filament exits the die and is deposited in a multilayer shape to form the desired article. The deposition rate can be controlled by changing the filament supply rate, cross-sectional dimensions, and the movement speed of the die head and / or the article. Therefore, one aspect of the present invention relates to a 3D printed article in which a resin composition for 3D printing is formed by the deposition of one or more lines by fused filament deposition.

[0098] The manufacture of articles using 3D printing can also be achieved by directly extruding pelletized 3D printing resin compositions using an extruder. In this method, the pellets are introduced into a heated extruder, and the molten 3D printing resin composition is extruded linearly from the extruder, depositing it into a multi-layered shape to form the desired article.

[0099] In the manufacturing of articles using 3D printing, to suppress warping of parts caused by the substrate (base) in contact with the printing device, or to improve adhesion to the substrate, an adhesive may be applied to the substrate or a protective covering such as masking tape may be applied before layering. Examples of adhesives include known adhesives such as Dimafix (registered trademark) from DIMA 3D, Printafix (registered trademark) from AprintaPro GmbH, and 3DLCA (registered trademark) from 3DLCA. Examples of masking tapes include heat-resistant polyimide films such as Kapton Tape from Toray DuPont Co., Ltd., Scotch Painter's Tape from 3M, Piolan Tape from Diatex Co., Ltd., and Build Tape for HP Filament(R) Super Flexible Type for 3D Printers from Hotty Polymer Co., Ltd. In addition, to obtain a similar effect, a substrate made of the same resin as the layering material, such as polypropylene, polyethylene, or ABS, can be used, and layering can also be done on a substrate with uneven surfaces. [Examples]

[0100] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The evaluation methods and resins used in the examples and comparative examples are as follows. Unless otherwise specified, the organic solvents used in the examples and comparative examples were purified by dehydration and removal of impurities.

[0101] I. Various analyzes 1. Melting peak temperature (Tm, unit: °C) and heat of fusion (ΔH, unit: J / g) A differential scanning calorimeter (DSC, TA Instruments "Q2000") was used. 4.8 to 5.2 g of the sample was weighed into a dedicated pan and placed in the measurement unit. The sample temperature was raised to 200°C and allowed to stand for 5 minutes. Then, the temperature was lowered to 40°C at a rate of 10°C / min, and the temperature was measured again at a rate of 10°C / min. The temperature at the endothermic peak top was defined as the melting peak temperature (Tm). The unit is °C. The total amount of heat of fusion observed during the heating from 40°C to 200°C was defined as ΔH.

[0102] 2. Melt Flow Rate (MFR, unit: g / 10 min) Measurements were taken in accordance with JIS K7210:2014, Method A, Condition M (230°C, 2.16 kg load).

[0103] 3. Comonomer content The ethylene and butene content of the copolymer is determined based on the method disclosed in the aforementioned Japanese Patent No. 6863174. 13 The intensity was determined from the integrated intensity obtained by 13C-NMR measurement. The sample preparation and measurement conditions are as follows. <Sample preparation conditions> 200 mg of the sample was placed in a 10 mm diameter NMR sample tube along with 2.4 mL of o-dichlorobenzene (ODCB) / deuterated bromide benzene (C6D5Br) = 4 / 1 (volume ratio) and hexamethyldisiloxane (1.98 ppm), which is the reference substance for chemical shift, and uniformly dissolved using a block heater at 150°C. <Device and 13 C-NMR measurement conditions> • Equipment: AV400 NMR spectrometer manufactured by Bruker BioSpin, Inc. • Probe: 10mm diameter cryoprobe ·Measurement temperature: 120℃ • Pulse angle: 90° • Pulse interval: 20 seconds • Total number of times: 512 • Decoupling condition: Broadband decoupling method

[0104] 4. Average length of filler material (B) (unit: mm) The average length of the filler (B) present in the 3D modeling resin composition pellets or the modeled object made using them was determined as follows. 3 to 7 g of a 3D modeling resin composition pellet containing glass fibers was placed in an electric furnace (Phoenix Microwave Furnace, manufactured by CEM Corporation) set to an ambient temperature of 600°C for 2 hours to remove the resin portion by incineration. The resulting residue was then mixed with a surfactant-containing solution made by adding 2 or 3 drops of Arabic Yamato glue to 2.6 L of water. A sample for observation was prepared by dropping and diffusing this mixed solution onto a thin glass plate. Using this sample, the length of more than 500 glass fibers was measured using a digital microscope (VHX-900, manufactured by Keyence Corporation), and the average value was determined as the average length. Furthermore, the 3D printing resin composition containing carbon fibers was prepared in the same manner as the 3D printing resin composition pellets containing glass fibers described above, except that the ambient temperature was 450°C and the standing time was 40 minutes, and the average length of the carbon fibers was determined. The average length of the filler material in the printed objects in the following examples and comparative examples is shown in Table 1.

[0105] II. Polymer Production 1. Manufacturing of PP1 (Copolymer (A)) (1) Preparation of the catalyst (1-a) Chemical treatment of silicates 350.0 g of distilled water was added to a 1 L flask equipped with a stirring blade and reflux device, and 280.3 g of 96% sulfuric acid was added dropwise. The aqueous solution was heated in an oil bath until its internal temperature reached 92°C. Once the target temperature was reached, 100.0 g of commercially available montmorillonite granulated particles (manufactured by Mizusawa Chemical Industries, Ltd., Benclay SL, particle size 18 μm) were added, and the mixture was reacted for 420 minutes while maintaining the temperature at 92°C. The reaction was stopped by adding 500 mL of distilled water to the reaction solution, and the resulting slurry was filtered using an apparatus with an aspirator connected to a Nutsch and suction bottle. Further, 1000 g of distilled water was added to the filtered cake to form a slurry, which was then filtered and washed again. This washing procedure was repeated a total of four times. After washing, the recovered cake was dried overnight at 110°C. After drying, before use as a catalyst component, the dried cake was crushed by lightly pressing it with a spatula, coarse material was removed by passing it through a 53 μm sieve, and it was further dried at 200°C under reduced pressure for 2 hours. From this, 71.8 g of chemically treated dried silicate was obtained.

[0106] (1-b) Preparation of solid catalyst components Under nitrogen, 20.0 g of the above-mentioned dried silicate and 72 mL of heptane were added to a 1 L flask and stirred. Then, 128 mL of heptane solution of trin-normal octyl aluminum (TnOA) (50.2 mmol of aluminum) was added and stirred at room temperature for 1 hour. After that, the mixture was washed with heptane until the residual volume was 1 / 100, and finally, 214 mL of heptane was added. Furthermore, under nitrogen, 218 mg (300 μmol) of dimethylsilylenebis[1,1'-{2-methyl-4-(4-chlorophenyl)-4H-azlenyl}]zirconium dichloride, 85 mL of heptane, and 1.04 mL of heptane solution of triisobutylaluminum (TiBA) (751 μmol in terms of aluminum) were added to a separate flask (200 mL volume), and the mixture was stirred at room temperature for 30 minutes to prepare a metallocene complex slurry. Next, the metallocene complex slurry was added to the 1L flask containing the previously mentioned dry silicate slurry, and the mixture was stirred at room temperature for 30 minutes.

[0107] (1-c) Prepolymerization After 30 minutes, 100 mL of heptane was added to the 1 L flask, and the entire slurry in the flask was transferred to a 1 L stirring autoclave that had been thoroughly purged with nitrogen. After transfer, the slurry temperature was raised to 40°C while stirring, and propylene was supplied at a rate of 10 g / h for 4 hours to perform preliminary polymerization. After stopping the supply of propylene, stirring was continued for another hour. Subsequently, the remaining monomer was purged, and the preliminary polymerization catalyst slurry was recovered from the autoclave. The recovered pre-polymerization catalyst slurry was allowed to stand, and the supernatant was removed. 16.5 mL of heptane solution of TiBA (11.9 mmol of aluminum) was added at room temperature, and then the mixture was dried under reduced pressure to obtain solid catalyst component (A). This solid catalyst component (A) contained 1.9 g of polypropylene per gram of solid component.

[0108] (2) Polymerization (Propylene ethylene random copolymerization) After thoroughly replacing the dried 200L volume agitated autoclave with propylene, 45 kg of liquefied propylene was added. To this, 1000 ml (0.24 mol) of TiBA heptane solution was added, and hydrogen and ethylene were added in molar ratios of hydrogen / propylene = 2.0 × 10⁻⁶. -4 The ethylene / propylene ratio was set to 0.15, and the internal temperature was maintained at 30°C. Next, 2.0 g of the solid catalyst component (A) from 1.(iii) above was injected into the autoclave under pressure with argon to start polymerization, and the temperature was raised to 70°C over 30 minutes, and that temperature was maintained for another hour. After 1 hour, 100 ml of ethanol was added to stop the polymerization. The remaining gas was purged, and 20 kg of propyleneethylene random copolymer (PP1) powder was obtained. Various analyses were performed on the obtained copolymer (PP1), revealing an ethylene content of 3.2% by weight, a melting peak temperature of 123.8°C, a ΔH of 71.2 J / g, and an MFR of 2 g / 10 min.

[0109] 2. Manufacturing of PP2 (Copolymer (A)) (1) Prepolymerization treatment A slurry containing 90 g of solid component (a) (a solid catalyst component consisting of THC-C-125, titanium, magnesium, and halogens, purchased from Toho Titanium Co., Ltd.) and 1.5 L of n-heptane, with a concentration of 60 g / L, was added to a 3 L autoclave equipped with a stirring device that was thoroughly purged with nitrogen. Then, while stirring, 10 g of n-heptane dilution of Et3Al was added as Et3Al. The temperature of the contents was set to 30°C, and then 270 g of propylene was supplied to the autoclave over 3 hours to allow the reaction to proceed. After the supply of propylene was completed, the reaction was continued for another 10 minutes. After the reaction, the resulting slurry was removed from the autoclave, and the reaction products were thoroughly washed with n-heptane. Then, vacuum drying was performed to obtain solid catalyst component (B). This solid catalyst component (B) contained 2.0 g of polypropylene per gram of solid component.

[0110] (2) Polymerization (propylene-ethylene-1-butene copolymerization) A horizontal polymerizer (L / D=4.3, internal volume 100 liters) equipped with stirring blades was supplied with solid catalyst component (B) at a rate of 0.29 g / h, Et3Al at a rate of 2.7 g / h, and (i-Pr)2Si(OMe)2 at a rate of 2.8 g / h. The reaction temperature was set to 58°C-61°C-64°C from the upstream side, for each of the three equally divided volumes of the polymerization reactor. While maintaining a reaction pressure of 1.90 MPa and a stirring speed of 28 rpm, hydrogen, ethylene, and 1-butene were continuously supplied to the horizontal reactor to maintain the hydrogen / propylene (molar ratio) in the gas phase of the polymerizer at 0.133, the ethylene / propylene (molar ratio) at 0.017, and the 1-butene / propylene (molar ratio) at 0.110, thereby controlling the polymer's MFR, ethylene content, and 1-butene content. The reaction heat was removed by the heat of vaporization of the continuously supplied liquefied propylene. The unreacted gas discharged from the reactor was cooled and condensed outside the reactor system and refluxed. The resulting polymer was continuously withdrawn through piping equipped with a blow case so that the polymer retention level was 50% of the reaction volume. The production rate of propylene-ethylene-1-butenotheraplast in this polymerization reaction was 10 kg / h. The catalytic activity, determined from the feed rate of the solid catalyst component (0.29 g / h) and the production rate of propylene-ethylene-1-butenotheraplast (10 kg / h), was approximately 34,000 g / g-catalyst. Various analyses were performed on the copolymer (PP2) obtained from this polymerization, and it was found that the ethylene content was 2.8% by weight, the butene content was 8.0% by weight, the melting peak temperature was 125.1°C, the ΔH was 66.8 J / g, and the MFR was 5 g / 10 min.

[0111] 3. Production of PP3 (1) Preparation of catalyst (1-a) Preparation of solid components A 10 L autoclave equipped with a stirring device was thoroughly purged with nitrogen, and 2 L of toluene was introduced. 200 g of diethoxymagnesium (Mg(OEt)2) and 1 L of TiCl4 were added at room temperature. The temperature was raised to 90°C while stirring, and 50 ml of di-n-butyl phthalate was introduced. The temperature was then raised to 110°C and the reaction was carried out for 3 hours. Afterward, the reaction product was thoroughly washed with toluene. Next, toluene was added to adjust the total volume to 2 L. 1 L of TiCl4 was added at room temperature, and the temperature was raised to 110°C and the reaction was carried out for 2 hours. After the reaction was complete, the reaction product was thoroughly washed with toluene. After washing, toluene was added to adjust the total volume to 2 L. 1 L of TiCl4 was added at room temperature, and the temperature was raised to 110°C and the reaction was carried out for 2 hours. Afterward, the reaction product was thoroughly washed with toluene. Finally, toluene was replaced with n-heptane to obtain a slurry of the solid components. When a portion of this slurry was sampled and analyzed, the Ti content of the solid component was found to be 2.7% by weight. Next, a 20L autoclave equipped with a stirring device was thoroughly purged with nitrogen, and 100g of the slurry of the solid components was introduced as the solid component. n-heptane was introduced to adjust the concentration of the solid component to 25g / L. 50ml of SiCl4 was added to this slurry while stirring, and the reaction was carried out at 90°C for 1 hour. After that, the reaction product was thoroughly washed with n-heptane. After washing, n-heptane was introduced to adjust the liquid level to 4 L. To this, 30 ml of dimethyldivinylsilane, 30 ml of diisobutyldimethoxysilane ((i-Pr)2Si(OMe)2), and 80 g of a diluted solution of triethylaluminum (Et3Al) in n-heptane were added as Et3Al, and the reaction was carried out at 40°C for 2 hours. Subsequently, the reaction product was thoroughly washed with n-heptane, and a portion of the slurry after washing was sampled, dried, and analyzed. The solid components contained 1.2% by weight of Ti and 8.8% by weight of (i-Pr)2Si(OMe)2.

[0112] (1-b) Prepolymerization n-heptane was added to the slurry described above to adjust the concentration of the solid component to 20 g / L. Next, the slurry was cooled to 10°C, and 10 g of a diluted n-heptane solution of Et3Al was added as Et3Al. 280 g of propylene was then supplied over 4 hours to allow the reaction to proceed. After the supply of propylene was complete, the reaction was continued for another 30 minutes. Subsequently, the gas phase was thoroughly purged with nitrogen, and the reaction product was thoroughly washed with n-heptane. The obtained slurry was removed from the autoclave and vacuum-dried to obtain solid catalyst component (C). This solid catalyst component contained 2.5 g of polypropylene per gram of solid component. Furthermore, in the portion of solid catalyst component (C) excluding the polypropylene, 1.0 wt% of Ti and 8.2 wt% of (i-Pr)2Si(OMe)2 were present.

[0113] (2) Polymerization (Propylene homopolymerization) A horizontal polymerizer (L / D=4.3, internal volume 100 liters) equipped with stirring blades was supplied with 0.50 g / h of the above solid catalyst component (C) and 4.7 g / h of Et3Al, respectively. The reaction temperatures were set to 58°C-61°C-64°C from the upstream side, for each of the three equally divided volumes of the polymerization reactor. While maintaining a reaction pressure of 1.90 MPa and a stirring speed of 28 rpm, hydrogen gas was continuously supplied to the horizontal reactor to control the molecular weight of the polymer, so that the hydrogen / propylene (molar ratio) of propylene and hydrogen in the gas phase of the polymerizer was maintained at 0.005. The heat of reaction was removed by the heat of vaporization of the continuously supplied liquefied propylene. Unreacted gas discharged from the reactor was cooled and condensed outside the reactor system and refluxed. The generated polymer was continuously extracted through piping equipped with a blow case so that the polymer retention level was 50% of the reaction volume. The production rate of propylene homopolymer at this time was 10 kg / h, and the catalytic activity of the propylene polymerization catalyst, determined from the amount of solid catalyst component fed per hour (0.50 g / h) and the production rate of propylene homopolymer (10 kg / h), was approximately 20,000 g / g-catalyst. Various analyses were performed on the polymer (PP3) obtained by this polymerization reaction, and it was found that the melting peak temperature was 164.8°C, ΔH was 105.7 J / g, and MFR was 1 g / 10 min.

[0114] 4. Manufacturing of PP4 (1) Catalytic synthesis (1-a) Preparation of solid components A 10 L autoclave equipped with a stirring device was thoroughly purged with nitrogen, and 2 L of toluene was introduced. 200 g of Mg(OEt)2 and 1 L of TiCl4 were added at room temperature. The temperature was raised to 90°C while stirring, and 50 ml of di-n-butyl phthalate was introduced. The temperature was then raised to 110°C and the reaction was carried out for 3 hours. After the reaction was complete, the reaction product was thoroughly washed with toluene. After washing, toluene was added to adjust the total volume to 2 L. 1 L of TiCl4 was added at room temperature, and the reaction was carried out at 110°C while stirring for 2 hours. The reaction product was then thoroughly washed with toluene. After washing, toluene was added to adjust the total volume to 2 L. 1 L of TiCl4 was added at room temperature, and the reaction was carried out at 110°C while stirring for 2 hours. The reaction product was then thoroughly washed with toluene. After washing, toluene was replaced with n-heptane to obtain a slurry of the solid components. A portion of this slurry was sampled and dried. Analysis revealed that the Ti content of the solid component was 2.7% by mass. Next, a 20 L autoclave equipped with a stirring device was thoroughly purged with nitrogen, and 100 g (0.056 mol of Ti) of the slurry of the above solid components was introduced as the solid component. Then, n-heptane was introduced to adjust the liquid level to 4 L. To this, 25 ml of dimethyldivinylsilane, 18 ml of t-butyldimethoxymethylsilane (t-Bu(Me)Si(OMe)2), and 40 g (0.35 mol) of a diluted n-heptane solution of Et3Al were added as Et3Al, and the reaction was carried out at 40°C for 2 hours. After that, the reaction product was thoroughly washed with n-heptane, and a portion of the resulting slurry was sampled, dried, and used as the solid component for analysis. Analysis of the solid components revealed that the slurry contained 1.8 mass% Ti and 8.8 mass% t-Bu(Me)Si(OMe)2. The molar ratio of Et3Al to Ti used in this process (Et3Al / Ti) was 6.3.

[0115] (1-b) Prepolymerization n-heptane was added to the slurry described above to adjust the concentration of the solid component to 20 g / L. After cooling the slurry to 10°C while stirring, 15 g (0.132 mol) of n-heptane diluted Et3Al was added as Et3Al, and 280 g of propylene was supplied over 4 hours to allow the reaction to proceed. After the supply of propylene was complete, the reaction was continued for another 30 minutes. Subsequently, the gas phase was thoroughly replaced with nitrogen, and the reaction product was thoroughly washed with n-heptane. The obtained slurry was removed from the autoclave and vacuum dried to obtain solid catalyst component (D). This solid catalyst component (D) contained 2.5 g of polypropylene per gram of solid content. In addition, the portion of solid catalyst component (D) excluding the polypropylene contained 1.5 mass% of Ti and 8.2 mass% of t-Bu(Me)Si(OMe)2. The molar ratio of triethylaluminum / Ti in this process was 3.5, and the molar ratio of Et3Al to Ti used throughout the entire process (Et3Al / Ti) was 6.3 + 3.5 = 9.8.

[0116] (2) Polymerization (propylene-based block copolymerization) (2-a) First polymerization step Polymerization was carried out using a continuous reactor consisting of two fluidized bed reactors (reactor 1 and reactor 2) with an internal volume of 2000 L, connected together. In reactor 1, a mixed gas was continuously supplied to maintain a polymerization temperature of 60°C, a total pressure of 3.0 MPa, a propylene partial pressure of 1.8 MPa, and an ethylene / propylene (molar ratio) of 0.009 in the gas phase of the reactor. Furthermore, hydrogen gas was continuously supplied as a molecular weight control agent to maintain a hydrogen / propylene (molar ratio) of 0.01 in the gas phase of the reactor. Solid catalyst component (D) was continuously supplied at a rate of 140 g / h (excluding the polypropylene component included by prepolymerization), and Et3Al at a rate of 4 kg / h to polymerize the propyleneethylene random copolymer. When a portion of the copolymer obtained in this first polymerization step was extracted and analyzed, the ethylene content was found to be 0.3% by weight.

[0117] (2-b) Second polymerization step Following the first polymerization step, the propylene-ethylene random copolymer from the first polymerization step was intermittently supplied to the second reaction vessel, which was connected to the first reaction vessel, to carry out the polymerization of the second polymerization step (continuous polymerization). In the second reaction vessel, a mixed gas was continuously supplied at a polymerization temperature of 80°C, a total pressure of 1.6 MPa, a propylene partial pressure of 1.1 MPa, and to maintain an ethylene / propylene (molar ratio) of 0.48 in the gas phase of the reaction vessel. Furthermore, hydrogen as a molecular weight control agent was continuously supplied, with the molar ratio of hydrogen gas adjusted so that the hydrogen concentration in the gas phase was 300 ppm. Ethyl alcohol was then supplied as an activity inhibitor (catalyst killer) so that the polymerization ratio in the second reaction vessel was 54% of the total product. The resulting copolymer was finally transferred to a downstream vessel connected to the second reaction vessel, where the reaction was stopped by supplying nitrogen gas containing moisture, and the residual gas was purged to obtain a propylene-based block copolymer (PP4). Various analyses were performed on the obtained copolymer (PP4), revealing an ethylene content of 22% by weight, a melting peak temperature of 162.4°C, a ΔH of 58.8 J / g, and a MFR of 1 g / 10 min.

[0118] 5. Manufacturing of PP5 Hydrogen / Propylene (molar ratio) = 2.2 × 10⁻⁶ -3 Polymerization was carried out in the same manner as in Example 1, except that 1.2 g of solid catalyst component (A) was used, to obtain 21 kg of propylene-based random copolymer (PP5) powder. Various analyses were performed on the obtained copolymer (PP5), revealing an ethylene content of 2.8% by weight, a melting peak temperature of 125.7°C, a ΔH of 69.4 J / g, and an MFR of 25 g / 10 min.

[0119] [Filler (B)] Glass fiber: Manufactured by Nippon Electric Glass Co., Ltd. Product name: ECS03T-480H, Strand Length: 3.0±1.0mm

[0120] [Compatibilizer (C)] Modified polyolefin: Manufactured by Mitsubishi Chemical Corporation. Product name: Modic P928 (Acid modification amount = greater than 0% and less than 10% by weight)

[0121] [Other ingredients] Elastomer 1: ExxonMobil, product name Vistamaxx 6102 (VM 6102). MFR = 3g / 10 min, no endothermic peak was observed. Elastomer 2: Manufactured by Mitsui Chemicals, product name Toughmer DF605. MFR = 0.9g / 10 min, no endothermic peak was observed.

[0122] III. Examples and Comparative Examples 1-1. Preparation of resin compositions for 3D modeling The resin composition for 3D modeling was prepared using the formulation shown in Table 1. Copolymer (A), compatibilizer (C), and other components were supplied to a twin-screw kneader (manufactured by Kobe Steel, Ltd., product name: KTX44) preheated to 200°C, and melt-kneaded at a screw rotation speed of 300 rpm and a discharge rate of 21 kg / hour. Filler (B) was side-fed from the middle of the extruder at a discharge rate of 9 kg / hour, and the strand obtained from the die outlet at a discharge rate of 30 kg / hour was water-cooled and then cut to obtain pellets.

[0123] 1-2. Formation of 3D objects A 3D object was fabricated using a material extrusion 3D printing system (S-Lab Co., Ltd., GEM800S, nozzle diameter 2mm). The pellets prepared above were fed into the hopper as the material, and the material was heated to 200°C and melted in the subsequent cylinder section. The fabrication speed was set to 2000 mm / min, the layer pitch to 1 mm, and the thickness of the fabricated object to 2.5 ± 0.2 mm. Based on the 3D coordinate data, the molten material was sequentially layered onto a substrate heated to 80°C and covered with Diatex Co., Ltd.'s product name: Piolan Tape K-10-RE, thereby fabricating a rectangular prism-shaped 3D object with dimensions of 100 mm in length, 100 mm in width, and 100 mm in height. The obtained 3D object was left to stand on the substrate at room temperature for at least 30 minutes after fabrication, cooled to room temperature, and then used for the following evaluations.

[0124] 2. Evaluation of 3D Modeled Objects 2-1. Evaluation of Shape Accuracy For each example of the rectangular parallelepiped 3D printed object on the substrate obtained above, the distance between each of the four vertices on the base surface in the vertical direction from the substrate was measured using calipers, and the average of these distances was used as the amount of warping to evaluate the shape accuracy. The evaluation results are shown in Table 1. ○: Average curvature is 0.4 mm or less △: Average curvature is greater than 0.4 mm but less than 0.6 mm. ×: Average curvature is 0.6mm or more

[0125] 2-2. Evaluation of Appearance and Characteristics For each of the 3D printed objects obtained above, a rectangular test piece measuring 10 mm wide x 10 mm high was cut from a 100 mm wide x 100 mm high surface using a desktop diamond saw machine (manufactured by Luxo Co., Ltd., product name: V-22). Using a digital microscope (manufactured by Keyence Corporation, product name: VHX-5000), the surface irregularities and fuzziness of the strands constituting each layer were evaluated at a magnification of 20x, focusing on the area approximately 50mm from the bottom surface of the test specimen obtained above. An example of the appearance of the fabricated object is shown in Figure 1. (1) Surface irregularities ○: The layered surface of the strands is observed to be uniform, and there is no white roughness. ×: Rough, uneven irregularities occur on the layered surface of the strands, and a white glare is observed unevenly. (2) Surface fuzzing ○: When the test specimen is observed from a direction perpendicular to the layered surface of the strand, no filler material is observed, and the surface is smooth. ×: When the test specimen is observed perpendicular to the laminated surface of the strand, the filler material protrudes from various points, and the surface is uneven.

[0126] 2-3. Evaluation of inter-laminated resin adhesion (tensile strength and fracture strain) For each of the 3D printed objects obtained above, a rectangular test piece measuring 15 mm wide x 100 mm high was cut from a 100 mm wide x 100 mm high surface using a desktop diamond saw machine (manufactured by Luxo Co., Ltd., product name: V-22). The thickness (in mm) of the test piece at its center was confirmed using a Digimatic standard outside micrometer (manufactured by Mitutoyo Corporation, product name: MDC-25SX). The test specimens obtained above were subjected to tensile testing using the Autograph precision universal testing machine (manufactured by Shimadzu Corporation, product name: AG-X plus) at a grip distance of 75 mm and a tensile speed of 5 mm / min to obtain the maximum tensile strength (unit: MPa) and fracture strain (unit: %). The evaluation of the maximum tensile strength and fracture strain was as follows, and the evaluation results are shown in Table 1. [Maximum tensile strength] ○: Maximum tensile strength of 10 MPa or more △: Maximum tensile strength is between 7 MPa and 10 MPa ×: Maximum tensile strength is less than 7 MPa [Tensile elongation at breaking] ○: Tensile fracture strain of 5% or more △: Tensile fracture strain is 4% or more but less than 5% ×: Tensile fracture strain is less than 4%

[0127] 2-4. Strength evaluation (flexural modulus) Using an injection molding machine (Toshiba Machine Co., Ltd., EC30 type injection molding machine) and the following molds, strip-shaped test pieces for physical property evaluation were prepared under the following conditions and used to evaluate the "flexural modulus of elasticity". • Mold: Two rectangular test pieces (10 x 80 x 4t (mm)) for physical property evaluation are molded. Molding conditions: Molding temperature 220°C, mold temperature 30°C, injection pressure 50 MPa, injection time 5 seconds, cooling time 20 seconds. Using the strip-shaped test specimens prepared as described above, the flexural modulus (unit: MPa) was measured at a test temperature of 23°C in accordance with JIS K7171. The criteria for determining the flexural modulus are as follows, and the evaluation results are shown in Table 1. [Flexural modulus] ○: Flexural modulus of elasticity is 1,200 MPa or higher ×: Flexural modulus less than 1,200 MPa

[0128] [Table 1] In Table 1, a "-" in the evaluation of Comparative Example 5 indicates that evaluation was not possible because a 3D printed object could not be obtained.

[0129] As shown in Table 1, three-dimensional molded objects containing the specific three-dimensional molding resin composition exhibit excellent shape accuracy and appearance, while also achieving high inter-layer adhesion. Even when using not only copolymer (A) as in Examples 1 and 8, but also propylene homopolymer, propylene block copolymer, and thermoplastic elastomer as a third component, as in Examples 4-7, the same good effects as in Examples 1 and 8 were observed. Furthermore, similarly good effects were observed regardless of the content of filler (B) (Examples 1-3). On the other hand, Comparative Examples 1-7, which did not contain the specific three-dimensional molding resin composition, showed poor balance in these performance aspects and were inferior. Examples 1, 4-8 showed significantly better shape accuracy and interlayer resin adhesion compared to Comparative Examples 6 and 7, which did not contain copolymer (A), and exhibited a good balance of shape accuracy, appearance, interlayer resin adhesion, and mechanical properties. Examples 1, 4-8 also showed superior appearance compared to Comparative Examples 1 and 4, which did not contain copolymer (A), and exhibited a good balance of shape accuracy, appearance, interlayer resin adhesion, and mechanical properties. Furthermore, Examples 1 and 2 showed high fracture strain compared to Comparative Examples 2 and 3, which did not contain compatibilizer (C), and exhibited a good balance of shape accuracy, appearance, interlayer resin adhesion, and mechanical properties. In Comparative Example 5, however, strands were not laminated during the fabrication of the 3D object, and a 3D structure could not be obtained.

Claims

1. A propylene-based random copolymer (A) having the following characteristics (A-i) to (A-iii), containing propylene and at least one of ethylene or an olefin having 4 to 10 carbon atoms, A filler (B) which is at least one of an inorganic filler or an organic filler, and Contains a compatibilizer (C), When the total weight of the propylene-based random copolymer (A) and the filler (B) is taken as 100% by weight, (A) is 40% to 99% by weight, and (B) is 1% to 60% by weight, A resin composition for three-dimensional molding, characterized in that it contains (C) in an amount of 0.1 parts by weight or more when the total weight of (A) and (B) is 100 parts by weight. Characteristic (A-i): The melting peak temperature measured by the DSC method is between 110°C and 150°C. Characteristic (A-ii): The heat of fusion measured by the DSC method is 80 J / g or less. Characteristics (A-iii): The melt flow rate (MFR) at 230°C and a load of 2.16 kg is 0.1 g / 10 min to 15 g / 10 min.

2. The resin composition for three-dimensional molding according to claim 1, characterized in that the filler (B) is at least one selected from talc, calcium carbonate, calcined kaolin, glass fiber, wood powder, cellulose powder, carbon fiber, and cellulose fiber.

3. The resin composition for three-dimensional molding according to claim 1, characterized in that the compatibilizer (C) is at least one selected from acid-modified polyolefins and hydroxy-modified polyolefins.

4. The resin composition for three-dimensional molding according to claim 1, characterized in that the filler (B) is fibrous, and the copolymer (A), the filler (B), and the compatibilizer (C) are melt-kneaded at 200°C, a screw rotation speed of 300 rpm, and a discharge rate of 21 kg / hour, and after cooling, the average length of the filler (B) measured with a digital microscope is 0.1 mm or more and 2.5 mm or less.

5. The resin composition for three-dimensional molding according to claim 1, characterized in that the filler (B) is glass fiber.

6. A three-dimensional object comprising the resin composition for three-dimensional molding described in any one of claims 1 to 5.

7. A method for producing a resin composition for three-dimensional molding according to any one of claims 1 to 5, characterized by comprising the step of melt-kneading a propylene-based random copolymer (A), a filler (B), and a compatibilizer (C) to obtain a melt-kneaded resin composition.

8. A method for manufacturing a three-dimensional object, characterized by comprising a method for manufacturing the resin composition for three-dimensional molding described in claim 7.

9. A method for manufacturing a three-dimensional object according to claim 8, characterized by comprising the steps of supplying the molten-mixed resin composition to the raw material supply section of a three-dimensional object manufacturing apparatus, melting it in the heating section of the three-dimensional object manufacturing apparatus, extruding it from a nozzle which is the discharge section of the three-dimensional object manufacturing apparatus, and layering it to form a three-dimensional object.

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