Filament for 3D modeling

Abstract

The present invention pertains to a filament for three-dimensional printing, the filament containing an olefin-based resin composition (α) satisfying 700≥24×ΔHc(α)-E'(α). ΔHc(α) is the heat of crystallization (J / g) of the olefin-based resin composition (α) as measured at a cooling rate of 10 °C / min by a differential scanning calorimeter, and E'(α) is the storage modulus (MPa) of the olefin-based resin composition (α) as measured with 10 Hz at 40°C.

Description

[Technical field]

[0001] The present invention relates to a filament for three-dimensional modeling, a resin molded product, a wound product, and a cartridge for three-dimensional modeling. [Background technology]

[0002] Extrusion-based thermal layer deposition systems are systems commonly referred to today as three-dimensional printers (3D printers), such as the thermal layer deposition system manufactured by Stratasys Inc. in the United States. Extrusion-based thermal layer deposition systems are used to extrude a flowable material from a nozzle part on an extrusion head to build a three-dimensional object layer by layer based on a computer-aided design (CAD) model.

[0003] Among them, the fused deposition modeling (ME) method is a simple system in which a raw material made of a thermoplastic resin is inserted as a filament into an extrusion head, and while being heated and melted, it is continuously extruded from a nozzle part of the extrusion head onto an XY-plane base in a chamber, and the extruded resin is deposited and fused onto an already deposited resin laminate, and as it cools, it solidifies into one piece. Therefore, the ME method has become widely used. In the ME method, a three-dimensional object similar to a CAD model is constructed by repeating the extrusion process while the nozzle position relative to the base is usually raised in the Z-axis direction perpendicular to the XY plane (Patent Documents 1 and 2).

[0004] Conventionally, amorphous or thermoplastic resins that are difficult to crystallize, such as acrylonitrile-butadiene-styrene resins and polylactic acid, have been preferably used as raw materials for the ME method from the viewpoints of moldability and fluidity (Patent Documents 3 to 5).

[0005] Meanwhile, in recent years, in addition to the above plastics, crystalline resins such as polypropylene resins have also been considered for use as 3D modeling materials for the ME method. These have excellent heat resistance, chemical resistance, and strength. Therefore, there is a possibility that they can be widely used, including in industrial applications such as the modeling of products and manufacturing tools.

[0006] However, such polyolefin resins are generally prone to crystallization, and as a result, ME-based 3D modeling using polyolefin resins has problems with poor modeling properties, such as reduced adhesion between layers in the model and warping of the model (resin molded body) due to crystallization shrinkage.

[0007] In response to this, a three-dimensional modeling material using a low-crystalline polyolefin resin has been disclosed (Patent Document 6). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japan Special Publication No. 2003-502184 [Patent Document 2] Japan Special Publication No. 2003-534159 [Patent Document 3] Japan Special Publication No. 2010-521339 [Patent Document 4] Japanese Patent Application Publication No. 2008-194968 [Patent Document 5] International Publication No. 2015 / 037574 [Patent Document 6] Japanese Patent Publication No. 2017-197627 Summary of the Invention [Problem to be solved by the invention]

[0009] However, it is possible for low-crystalline polyolefin resins such as those described in Patent Document 6 to suppress the occurrence of molding defects such as warping due to crystallization shrinkage during 3D modeling and improve 3D modeling properties. Furthermore, the modeling properties of polyolefin resins at relatively low speeds such as 0.5 mm / s have been improved.

[0010] However, as a result of the study by the present inventors, it was found that the strength of the resin molded body and the hardness of the filament are insufficient when the low-crystalline polyolefin resin is crystallized, especially at around room temperature, because the elastic modulus is reduced by low crystallization. Therefore, the low-crystalline polyolefin resin as mentioned in Patent Document 6 is limited in the fields in which it can be applied, and a problem was found when the modeling speed was increased to improve productivity. Specifically, a new problem was found in that when the filament is sent to the extrusion head at high speed, as in the high-speed three-dimensional modeling of polyolefin resin, bending of the filament occurs, resulting in poor high-speed three-dimensional modeling.

[0011] Therefore, an object of the present invention is to provide a filament for 3D printing that does not warp the molded object (resin molded object) during 3D printing, and does not bend the filament even when the filament is fed to an extrusion head at high speed as in high-speed 3D printing, resulting in good high-speed 3D printing properties and excellent strength of the molded object (resin molded object).Another object of the present invention is to provide a resin molded object, a wound body, and a cartridge for 3D printing that contain the filament for 3D printing. [Means for solving the problem]

[0012] As a result of extensive investigations, the present inventors have concluded that the above problems can be solved by using a polyolefin resin composition having specific thermal properties and storage modulus.

[0013] That is, the gist of the present invention is as follows. <1> A filament for three-dimensional modeling, comprising an olefin-based resin composition (α) that satisfies the following formula [1]: 700≧24×ΔHc(α)-E´(α)···[1] ΔHc(α): Heat of crystallization (J / g) when the olefin resin composition (α) is measured with a differential scanning calorimeter at a temperature drop rate of 10° C. / min. E'(α): storage modulus (MPa) of the olefin resin composition (α) measured at 40°C and 10 Hz <2> The ΔHc(α) is 75 J / g or less; <1> The filament for three-dimensional modeling described in claim 1. <3> The E'(α) is 350 MPa or more. <1> or <2> The filament for three-dimensional modeling described in claim 1. <4> The olefin resin composition (α) contains an olefin resin composition (A) and a resin composition (B), The resin composition (B) has a heat of crystallization (ΔHc(B)) of less than 10 J / g when measured with a differential scanning calorimeter at a temperature decreasing rate of 10° C. / min. <1> ~ <3> 3. The filament for three-dimensional printing according to claim 1 . <5> the difference between the crystallization temperature of the olefin resin composition (A) measured at a temperature decreasing rate of 10° C. / min using a differential scanning calorimeter and the crystallization temperature of the olefin resin composition (α) measured at a temperature decreasing rate of 10° C. / min using a differential scanning calorimeter is 10° C. or less; <4> The filament for three-dimensional modeling described above. <6> The olefin resin composition (α) contains an olefin resin composition (A), The olefin resin composition (A) is at least one resin composition selected from the group consisting of a propylene homopolymer, a random copolymer of propylene and at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, a block copolymer of propylene and at least one monomer selected from ethylene and at least one monomer selected from α-olefin having 4 to 12 carbon atoms, a maleic anhydride grafted polypropylene, a blend of at least one of propylene and polyethylene with an ethylene-propylene rubber, a dynamically crosslinked product of at least one of propylene and polyethylene with an ethylene-propylene rubber, a polymer of at least one of propylene and polyethylene with an ethylene-propylene rubber, a high-density polyethylene, a low-density polyethylene, and a linear low-density polyethylene. <1> ~ <5> 3. The filament for three-dimensional printing according to claim 1 . <7> The olefin resin composition (α) contains a resin composition (B), The resin composition (B) contains a cyclic olefin resin. <1> ~ <6> 3. The filament for three-dimensional printing according to claim 1 . <8> Further containing a filler, <1> ~ <7> 3. The filament for three-dimensional printing according to claim 1 . <9> <1> ~ <8> A resin molded product comprising the filament for three-dimensional modeling according to any one of the above items. <10> <1> ~ <8> 2. A wound body of a filament for three-dimensional printing according to any one of claims 1 to 11. <11> <1> ~ <8> A cartridge for three-dimensional modeling, comprising the filament for three-dimensional modeling described in any one of claims 1 to 5. Effect of the Invention

[0014] According to the present invention, it is possible to provide a polyolefin-based filament for three-dimensional printing that does not warp the molded object (resin molded object) during three-dimensional printing, and does not bend the filament even when the filament is sent to an extrusion head at high speed as in high-speed three-dimensional printing, resulting in good high-speed three-dimensional printing properties and excellent strength of the molded object (resin molded object).Furthermore, according to the present invention, it is possible to provide a resin molded object, a wound body, and a cartridge for three-dimensional printing that contain the filament for three-dimensional printing.

[0015] [Reasons for the effectiveness of the invention] The reason why the present invention is effective is not yet clear, but it can be assumed that the reason is as follows. That is, the filament for three-dimensional modeling of the present invention has a low heat of crystallization, and therefore the filament for three-dimensional modeling of the present invention has a small amount of crystallization shrinkage and is suppressed from warping during three-dimensional modeling. In addition, the filament for three-dimensional modeling of the present invention has a high elastic modulus at around room temperature, which makes it possible to suppress bending of the filament during feeding.

[0016] In general polyolefin resins, the heat of crystallization is proportional to the modulus of elasticity near room temperature, so if the heat of crystallization is reduced in an attempt to suppress warping, the modulus of elasticity near room temperature decreases, making the filament more likely to bend, making it difficult to simultaneously suppress warping during modeling and suppress bending of the filament. However, the filament for 3D modeling of the present invention contains a specific resin, making it possible to simultaneously suppress warping and bending.

[0017] In addition, such an effect can be obtained, for example, by simply adding a filler to the filament. However, in this case, there is a concern that the filler inhibits interlayer adhesion between resins, and when three-dimensionally modeled, the strength in the perpendicular direction (Z-axis strength) to the interlayer of the modeled object (resin molded body) is reduced. On the other hand, the filament for three-dimensional modeling of the present invention contains a specific resin, and thus it is possible to achieve both a low crystallization shrinkage amount and a high room temperature elastic modulus while ensuring interlayer adhesion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out in various modifications within the scope of its gist.

[0019] The filament for three-dimensional modeling of the present invention is characterized by containing an olefin-based resin composition (α).

[0020] <Olefin-based resin composition (α)> The olefin resin composition (α) is characterized by satisfying the following formula [1]. The olefin resin composition (α) in the present invention contains an olefin resin and, if necessary, other resins, but excludes additives.

[0021] 700≧24×ΔHc(α)-E´(α)···[1] ΔHc(α): Heat of crystallization (J / g) when the olefin resin composition (α) is measured with a differential scanning calorimeter at a temperature drop rate of 10° C. / min. E'(α): storage modulus (MPa) of the olefin resin composition (α) measured at 40°C and 10 Hz

[0022] Here, by having “24×ΔHc(α)-E′(α)” be in the above range, warping during 3D modeling is suppressed, and bending during filament feeding can also be suppressed.

[0023] In addition, the upper limit of "24×ΔHc(α)-E'(α)" is not particularly limited, but from the viewpoint of achieving both high-speed formability and interlayer adhesion, it is preferably 500 or less, more preferably 300 or less, even more preferably 100 or less, particularly preferably 0 or less, even more preferably -100 or less, and most preferably -200 or less.

[0024] Furthermore, from the viewpoint of achieving both high speed molding and interlayer adhesion, the lower limit of "24×ΔHc(α)-E'(α)" is preferably -2000 or more, more preferably -1500 or more, even more preferably -1000 or more, particularly preferably -500 or more, and most preferably -300 or more.

[0025] ΔHc(α) is not particularly limited, but is usually 75 J / g or less, preferably 60 J / g or less, more preferably 55 J / g or less, even more preferably 50 J / g or less, particularly preferably 45 J / g or less, even more preferably 40 J / g or less, and most preferably 30 J / g or less. This can reduce warping of a molded object (resin molded product) due to crystallization shrinkage during three-dimensional molding.

[0026] From the viewpoint of heat resistance, ΔHc(α) is preferably 1 J / g or more, more preferably 5 J / g or more, even more preferably 8 J / g or more, particularly preferably 10 J / g or more, and most preferably 15 J / g or more.

[0027] In addition, ΔHc(α) can be adjusted by the resin composition and the blend ratio of the olefin resin composition (A) and the resin composition (B) described below.

[0028] E'(α) is not particularly limited, but is usually 350 MPa or more. If E'(α) is within this range, bending during filament feeding is suppressed, and the moldability is excellent, and the strength of the molded resin molded product is excellent. E'(α) is preferably 400 MPa or more, more preferably 500 MPa or more, even more preferably 800 MPa or more, particularly preferably 1000 MPa or more, and most preferably 1200 MPa or more.

[0029] Although there is no particular upper limit for E'(α), E'(α) is preferably 5000 MPa or less, more preferably 4500 MPa or less, even more preferably 4000 MPa or less, particularly preferably 3500 MPa or less, even more preferably 3000 MPa or less, and most preferably 2500 MPa or less. If E'(α) is within this range, the hardness of the filament becomes appropriate, and handling during modeling (setting the filament in a printer, etc.) is easy, which is preferable.

[0030] Furthermore, E'(α) can be adjusted by the resin composition and the blend ratio of the olefin resin composition (A) and the resin composition (B) described below.

[0031] The crystallization temperature (Tc(α)) of the olefin resin composition (α) measured with a differential scanning calorimeter at a temperature drop rate of 10°C / min is not particularly limited, but from the viewpoint of suppressing warping during molding, it is preferably 200°C or less, more preferably 150°C or less, even more preferably 120°C or less, particularly preferably 110°C or less, and most preferably 100°C or less.

[0032] From the viewpoint of heat resistance, Tc(α) is preferably 20° C. or higher, more preferably 40° C. or higher, even more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher.

[0033] Furthermore, Tc(α) can be adjusted by the resin composition, the blend ratio of the olefin resin composition (A) to the resin composition (B) described below, and the like.

[0034] The crystalline melting temperature (Tm(α)) of the olefin resin composition (α) measured at a heating rate of 10°C / min using a differential scanning calorimeter is not particularly limited, but from the viewpoint of ease of modeling using a general-purpose three-dimensional printer, it is preferably 300°C or less, more preferably 250°C or less, even more preferably 200°C or less, particularly preferably 150°C or less, and most preferably 140°C or less.

[0035] From the viewpoint of heat resistance, Tm(α) is preferably 20° C. or higher, more preferably 40° C. or higher, even more preferably 60° C. or higher, particularly preferably 80° C. or higher, and most preferably 100° C. or higher.

[0036] Furthermore, Tm(α) can be adjusted by the resin composition, the blend ratio of the olefin resin composition (A) to the resin composition (B) described below, and the like.

[0037] The olefin resin composition (α) preferably contains an olefin resin composition (A) and a resin composition (B) described below. The resin composition (B) has a heat of crystallization (ΔHc(B)) of less than 10 J / g when measured with a differential scanning calorimeter at a temperature drop rate of 10° C. / min.

[0038] In addition, the difference between the crystallization temperature (Tc(A)) of the olefin resin composition (A) measured at a temperature drop rate of 10°C / min using a differential scanning calorimeter and the crystallization temperature (Tc(α)) of the olefin resin composition (α) measured at a temperature drop rate of 10°C / min using a differential scanning calorimeter is not particularly limited, but is preferably 10°C or less, more preferably 8°C or less, even more preferably 6°C or less, particularly preferably 4°C or less, and most preferably 2°C or less.

[0039] That is, it is preferable that the crystallization of the olefin resin composition (A) is not easily inhibited by the resin composition (B), which results in excellent heat resistance of the resin molded product produced using the filament for three-dimensional modeling of the present invention.

[0040] <Olefin-based resin composition (A)> Here, the olefin resin composition (A) is not particularly limited, but specific examples include the following.

[0041] That is, propylene homopolymer, random copolymer of propylene and at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, block copolymer of propylene and at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, maleic anhydride grafted polypropylene, blend of at least one of propylene and polyethylene with ethylene-propylene rubber, dynamically crosslinked product of at least one of propylene and polyethylene with ethylene-propylene rubber (thermoplastic vulcanizates), polymerization product of at least one of propylene and polyethylene with ethylene-propylene rubber (reactor TPO), high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), etc.

[0042] Among these, from the viewpoint of heat resistance, preferred are propylene homopolymers, random copolymers of propylene and at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, block copolymers of propylene and at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, dynamically crosslinked products of at least one of propylene and polyethylene and ethylene-propylene rubber (thermoplastic vulcanizates), and polymers of at least one of propylene and polyethylene and ethylene-propylene rubber (reactor TPO).

[0043] The olefin resin composition (A) may consist of one resin selected from the above, or may consist of a combination of two or more resins selected from the above.

[0044] The crystallization heat (ΔHc(A)) of the olefin resin composition (A) measured with a differential scanning calorimeter at a temperature drop rate of 10°C / min is not particularly limited, but from the viewpoint of formability, it is preferably 120 J / g or less, more preferably 110 J / g or less, even more preferably 100 J / g or less, particularly preferably 85 J / g or less, and most preferably 70 J / g or less.

[0045] From the viewpoint of heat resistance, ΔHc(A) is preferably 10 J / g or more, more preferably 20 J / g or more, even more preferably 30 J / g or more, particularly preferably 40 J / g or more, and most preferably 50 J / g or more.

[0046] Here, the heat of crystallization (ΔHc) in the present invention is a value measured using a differential scanning calorimeter (DSC) in accordance with JIS K7122, when approximately 10 mg of a sample is heated from room temperature to a crystal melting temperature (Tm)+20°C or higher at a heating rate of 10°C / min, held at that temperature for 1 minute, and then cooled to 0°C at a cooling rate of 10°C / min.

[0047] The crystallization temperature (Tc(A)) of the olefin resin composition (A) measured with a differential scanning calorimeter at a temperature drop rate of 10°C / min is not particularly limited, but from the viewpoint of moldability, it is preferably 150°C or less, more preferably 140°C or less, even more preferably 130°C or less, particularly preferably 120°C or less, and most preferably 110°C or less.

[0048] Moreover, from the viewpoint of heat resistance, Tc(A) is preferably 40°C or higher, more preferably 60°C or higher, even more preferably 70°C or higher, particularly preferably 80°C or higher, and most preferably 90°C or higher.

[0049] In addition, Tc(A) can be adjusted by the composition and stereoregularity of the resin.

[0050] The crystalline melting temperature (Tm(A)) of the olefin resin composition (A) is not particularly limited, but from the viewpoint of heat resistance, it is preferably 100°C or higher, more preferably 110°C or higher, even more preferably 120°C or higher, particularly preferably 130°C or higher, and most preferably 135°C or higher.

[0051] There is no particular upper limit for Tm(A), and Tm(A) is generally preferably 200°C or lower, more preferably 195°C or lower, even more preferably 190°C or lower, particularly preferably 185°C or lower, and most preferably 180°C or lower.

[0052] Furthermore, Tm(A) can be adjusted by the composition and stereoregularity of the resin.

[0053] The storage modulus (E'(A)) of the olefin resin composition (A) measured at 40°C and 10 Hz is not particularly limited, but from the viewpoints of suppressing filament bending during shaping and the strength of the shaped resin molded product, it is preferably 100 MPa or more, more preferably 200 MPa or more, even more preferably 300 MPa or more, particularly preferably 350 MPa or more, and most preferably 400 MPa or more.

[0054] Moreover, from the viewpoint of handleability of the filaments, E'(A) is preferably 3000 MPa or less, more preferably 2000 MPa or less, even more preferably 1500 MPa or less, particularly preferably 1250 MPa or less, and most preferably 1000 MPa or less.

[0055] Furthermore, E'(A) can be adjusted by the composition and stereoregularity of the resin.

[0056] The olefin resin composition (α) preferably contains an olefin resin composition (A), and may contain a resin composition (B) described below, if necessary.

[0057] In addition, the filament for three-dimensional shaping of the present invention may contain, in addition to the olefin resin composition (α), a filler, other resins, and other additives described below. In this case, the content of the olefin resin composition (α) in the filament for three-dimensional shaping of the present invention is not particularly limited, but is usually 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, from the viewpoint of excellent heat resistance and shaping ability.

[0058] In addition, the content of the olefin-based resin composition (α) in the filament for three-dimensional modeling of the present invention is preferably 100% by mass or less, more preferably 99% by mass or less, even more preferably 98.5% by mass or less, and particularly preferably 98% by mass or less, from the viewpoint of the strength of the modeled object and imparting other functionality.

[0059] In addition, when the olefin resin composition (α) contains the olefin resin composition (A) and the resin composition (B) described below, the content of the olefin resin composition (A) in the olefin resin composition (α) is preferably 30 mass% or more, more preferably 40 mass% or more, even more preferably 50 mass% or more, particularly preferably 60 mass% or more, and most preferably 70 mass% or more, from the viewpoint of heat resistance.

[0060] In addition, the content of the olefin-based resin composition (A) in the olefin-based resin composition (α) is preferably 95 mass% or less, more preferably 90 mass% or less, even more preferably 85 mass% or less, particularly preferably 80 mass% or less, and most preferably 75 mass% or less, from the viewpoint of moldability.

[0061] <Resin composition (B)> The olefin resin composition (α) can contain a resin composition (B). Resin composition (B) is not particularly limited as long as the heat of crystallization (ΔHc(B)) measured with a differential scanning calorimeter at a temperature drop rate of 10° C. / min is less than 10 J / g. ΔHc(B) is preferably 9 J / g or less, more preferably 8 J / g or less, even more preferably 7 J / g or less, and particularly preferably 6 J / g or less, in view of ease of adjusting the heat of crystallization of the olefin resin composition (α).

[0062] The lower limit of ΔHc(B) is not particularly limited, but is 0 J / g or more, and from the viewpoint of heat resistance, 1 J / g or more is preferable, 1.5 J / g or more is more preferable, 2 J / g or more is even more preferable, and 2.5 J / g or more is particularly preferable.

[0063] Specific examples of the resin composition (B) include cyclic olefin resins, ABS (acrylonitrile-butadiene-styrene), MBS (methyl methacrylate-butadiene-styrene copolymer), PETG (Poly Ethylene Terephthalate Glycol-modified), PLA (polylactic acid), PC (polycarbonate), and the like.

[0064] Among them, from the viewpoint of kneadability with the olefin resin composition (A), a cyclic olefin resin is preferred. The cyclic olefin resin is an olefin resin having an alicyclic structure in the molecular chain. Examples of the alicyclic structure include monocyclic structures such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane, and bicyclic structures such as norbornane, decalin, and spiropentane. These may be in the polymer main chain or in the side chain, but are preferably in the side chain in order to further increase kneadability and heat fusion with the olefin resin composition (A).

[0065] Examples of the cyclic olefin resin include a copolymer of ethylene and a cyclic olefin (cycloalkene), a copolymer of an α-olefin and a cyclic olefin (cycloalkene), a ring-opening polymer of a cyclic olefin (cycloalkene), a hydrogenated product of a ring-opening polymer of a cyclic olefin, and a hydrogenated block copolymer which is a hydrogenated product of a block copolymer containing at least one type of aromatic vinyl monomer unit and at least one type of conjugated diene monomer unit.

[0066] Among them, from the viewpoint of kneadability with the olefin resin composition (A) and heat fusion property, the resin having an alicyclic structure in the side chain is preferably a hydrogenated block copolymer, which is a hydrogenated product of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit. The resin composition (B) may be composed of one resin selected from the above, or may be a combination of multiple resins selected from the above.

[0067] The hydrogenated block copolymer has a hydrogenated aromatic vinyl polymer block unit, which is a hydrogenated product of a polymer block composed of the aromatic vinyl monomer unit, and a hydrogenated conjugated diene polymer block unit, which is a hydrogenated product of a polymer block composed of the conjugated diene monomer unit. The hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit.

[0068] In this specification, the term "block" refers to a copolymer polymerization segment that exhibits microphase separation from structurally or compositionally distinct polymerization segments of the copolymer, as described below. Thus, for example, "having at least two block units" refers to the presence of at least two copolymer polymerization segments that exhibit microphase separation from structurally or compositionally distinct polymerization segments in the hydrogenated block copolymer.

[0069] The aromatic vinyl monomer serving as a raw material for the aromatic vinyl monomer unit is a monomer represented by the following general formula (1).

[0070] [ka]

[0071] In formula (1), R is a hydrogen atom or an alkyl group, and Ar is a phenyl group, a halophenyl group, an alkylphenyl group, an alkylhalophenyl group, a naphthyl group, a pyridinyl group, or an anthracenyl group.

[0072] The alkyl group may be a mono- or poly-substituted alkyl group with a functional group such as a halo group, a nitro group, an amino group, a hydroxyl group, a cyano group, a carbonyl group, or a carboxyl group. The number of carbon atoms in the alkyl group is preferably 1 to 6. The Ar is preferably a phenyl group or an alkylphenyl group, and more preferably a phenyl group.

[0073] Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene (including all isomers, especially p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, vinylanthracene (all isomers), and mixtures thereof.

[0074] The conjugated diene monomer serving as the raw material for the conjugated diene monomer unit is not particularly limited as long as it is a monomer having two conjugated double bonds.

[0075] Conjugated diene monomers include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3 pentadiene and the like, and mixtures thereof.

[0076] Polybutadiene, a polymer of 1,3-butadiene, can contain either the 1,2 configuration, which upon hydrogenation gives the equivalent of 1-butene repeat units, or the 1,4 configuration, which upon hydrogenation gives the equivalent of ethylene repeat units.

[0077] The hydrogenated polymerizable block composed of the aromatic vinyl monomer and the conjugated diene monomer including 1,3-butadiene is included in the hydrogenated block copolymer used in the present invention. Preferably, the hydrogenated block copolymer is a block copolymer having no functional groups. Here, "having no functional groups" means that there are no functional groups in the block copolymer, i.e., there are no groups containing elements other than carbon and hydrogen.

[0078] A preferred example of the hydrogenated aromatic vinyl polymer block unit is hydrogenated polystyrene, and a preferred example of the hydrogenated conjugated diene polymer block unit is hydrogenated polybutadiene. A preferred embodiment of the hydrogenated block copolymer is a hydrogenated triblock or pentablock copolymer of styrene and butadiene, which preferably does not contain any other functional group or structural modifier.

[0079] A "block" is defined as a polymeric segment of a copolymer that exhibits microphase separation from structurally or compositionally distinct polymeric segments of the copolymer. Microphase separation results from the immiscibility of polymeric segments in a block copolymer.

[0080] Microphase separation and block copolymers are discussed extensively in "Block Copolymers - Designer Soft Materials" in the February 1999 issue of PHYSICS TODAY, pp. 32-38.

[0081] The lower limit of the content (mol%) of the hydrogenated aromatic vinyl polymer block unit is preferably 30 mol% or more, more preferably 40 mol% or more, based on the cyclic polyolefin. The upper limit of the content (mol%) of the hydrogenated aromatic vinyl polymer block unit is preferably 99 mol% or less, more preferably 90 mol% or less, based on the cyclic polyolefin.

[0082] When the ratio of the hydrogenated aromatic vinyl polymer block units is equal to or more than the above lower limit, the rigidity does not decrease, and when it is equal to or less than the above upper limit, the brittleness does not increase.

[0083] The lower limit of the content of the hydrogenated conjugated diene polymer block unit is preferably 1 mol % or more, more preferably 10 mol % or more, based on the cyclic polyolefin, and the upper limit of the content of the hydrogenated conjugated diene polymer block unit is preferably 70 mol % or less, more preferably 60 mol % or less, based on the cyclic polyolefin.

[0084] When the ratio of the hydrogenated conjugated diene polymer block units is equal to or more than the above lower limit, brittleness does not increase, and when it is equal to or less than the above upper limit, rigidity does not decrease, so that the strength of the shaped resin molded article is excellent.

[0085] The hydrogenated block copolymers are prepared by hydrogenation of block copolymers including triblock, multiblock, tapered block, and star block copolymers such as SBS, SBSBS, SIS, SISIS, and SISBS (where S is polystyrene, B is polybutadiene, and I is polyisoprene).

[0086] The hydrogenated block copolymer contains a segment of an aromatic vinyl polymer at each end, and therefore the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units, and at least one hydrogenated conjugated diene polymer block unit between the two hydrogenated aromatic vinyl polymer block units.

[0087] The block copolymers that make up the hydrogenated block before hydrogenation may contain additional blocks, which may be attached at any position along the triblock polymer backbone. Thus, linear blocks include, for example, SBS, SBSB, SBSBS, and SBSBSB. The copolymers may be branched, and the polymer chains may be attached at any position along the backbone of the copolymer.

[0088] The lower limit of the weight average molecular weight (Mw) of the hydrogenated block copolymer is preferably 30,000 or more, more preferably 40,000 or more, even more preferably 45,000 or more, and particularly preferably 50,000 or more. The upper limit of the Mw of the hydrogenated block copolymer is preferably 120,000 or less, more preferably 100,000 or less, even more preferably 95,000 or less, particularly preferably 90,000 or less, most preferably 85,000 or less, and extremely preferably 80,000 or less.

[0089] When the Mw of the hydrogenated block copolymer is equal to or greater than the above lower limit, the mechanical strength does not decrease, and when it is equal to or less than the above upper limit, the moldability does not deteriorate. Mw herein is determined using gel permeation chromatography (GPC).

[0090] The hydrogenation levels of the block copolymer are preferably 90% or more of hydrogenated vinyl aromatic polymer block units and 95% or more of hydrogenated conjugated diene polymer block units, more preferably 95% or more of hydrogenated vinyl aromatic polymer block units and 99% or more of hydrogenated conjugated diene polymer block units, even more preferably 98% or more of hydrogenated vinyl aromatic polymer block units and 99.5% or more of hydrogenated conjugated diene polymer block units, and particularly preferably 99.5% or more of hydrogenated vinyl aromatic polymer block units and 99.5% or more of hydrogenated conjugated diene polymer block units.

[0091] The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the proportion of the aromatic vinyl polymer block unit saturated by hydrogenation, and the hydrogenation level of the conjugated diene polymer block unit indicates the proportion of the conjugated diene polymer block unit saturated by hydrogenation. Such a high level of hydrogenation is preferred for heat resistance and transparency.

[0092] The hydrogenation level of the vinyl aromatic polymer block units and the hydrogenation level of the conjugated diene polymer block units are determined using proton NMR.

[0093] The glass transition temperature (Tg) of the resin composition (B) is not particularly limited, but from the viewpoint of the strength and heat resistance of the filament and the resin molded product molded using it, it is preferably 50 ° C. or more, more preferably 70 ° C. or more, even more preferably 80 ° C. or more, particularly preferably 90 ° C. or more, and most preferably 100 ° C. or more. In addition, from the viewpoint of kneadability with the olefin resin composition (A) and moldability (warping suppression during molding), the glass transition temperature (Tg) of the resin composition (B) is preferably 200 ° C. or less, more preferably 180 ° C. or less, even more preferably 160 ° C. or less, particularly preferably 150 ° C. or less, and most preferably 140 ° C. or less.

[0094] The glass transition temperature (Tg) is a value measured using a differential scanning calorimeter (DSC) in accordance with JIS K7121, in which about 10 mg of a sample is heated from room temperature to 250°C at a heating rate of 10°C / min, held at that temperature for 1 minute, cooled to 30°C at a heating rate of 10°C / min, and then heated again to 250°C at a heating rate of 10°C / min.

[0095] The content of the resin composition (B) in the olefin resin composition (α) is preferably less than 70% by mass, more preferably less than 60% by mass, even more preferably less than 50% by mass, and more preferably less than 40% by mass from the viewpoint of heat resistance. Also, from the viewpoint of moldability, the content is preferably more than 5% by mass, more preferably more than 10% by mass, even more preferably more than 15% by mass, particularly preferably more than 20% by mass, and most preferably more than 25% by mass.

[0096] <Filament for 3D modeling> The olefin resin composition (α) may be used in a form suitable for the embodiment. Examples of the form include pellets, powder, granules, filaments, etc. Among these, it is preferable to use the composition in the form of filaments.

[0097] The filament for three-dimensional modeling of the present invention may contain, in addition to the olefin-based resin composition (α), fillers (organic particles, inorganic particles, reinforcing materials, etc.), other resins, and other components to the extent that the effects of the present invention are not impaired.

[0098] Fillers (organic particles, inorganic particles, reinforcing materials, etc.) are described in detail below. Other resins include PLA, polyester resins, polyamide resins, polyacetal resins, etc. Other components include heat resistance agents, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slip agents, crystal nucleating agents, tackifiers, sealability improvers, antifogging agents, mold release agents, plasticizers, pigments, dyes, fragrances, flame retardants, etc.

[0099] Specific examples of organic particles among the fillers include acrylic resin particles, melamine resin particles, silicone resin particles, and polystyrene resin particles.

[0100] Specific examples of inorganic particles among the fillers include silica, alumina, kaolin, titanium dioxide, calcium carbonate, magnesium carbonate, zinc carbonate, calcium stearate, magnesium stearate, and zinc stearate.

[0101] Here, specific examples of the reinforcing material among the fillers include inorganic fillers and inorganic fibers. Specific examples of inorganic fillers include calcium carbonate, zinc carbonate, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, potassium titanate, glass balloons, glass flakes, glass powder, silicon carbide, silicon nitride, boron nitride, gypsum, calcined kaolin, zinc oxide, antimony trioxide, zeolite, hydrotalcite, wollastonite, silica, talc, metal powder, alumina, graphite, carbon black, and carbon nanotubes.

[0102] Specific examples of inorganic fibers include cut glass fibers, milled glass fibers, glass fibers, gypsum whiskers, metal fibers, metal whiskers, ceramic whiskers, carbon fibers, and cellulose nanofibers.

[0103] Here, the content of the filler is not particularly specified, but from the viewpoint of the strength of the resin molded product to be molded, it is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on 100% by mass of the resin composition (α). Also, from the viewpoint of suppressing a decrease in interlayer adhesion of the resin molded product to be molded, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0104] <Method of manufacturing filaments for 3D modeling> The filament for three-dimensional shaping of the present invention is produced using the above-mentioned olefin resin composition (α). The method for mixing the olefin resin composition (α) is not particularly limited, but a known method, for example, a melt kneading device such as a single screw extruder, a multi-screw extruder, a Banbury mixer, or a kneader, can be used.

[0105] In the present invention, it is preferable to use a co-rotating twin screw extruder from the viewpoint of dispersibility and miscibility of each component, etc. Excellent dispersibility and miscibility are preferable because they can increase the precision of the filament diameter and the roundness.

[0106] The method for producing the filament for three-dimensional shaping of the present invention is not particularly limited, but it can be obtained by a method in which the above-mentioned olefin resin composition (α) is molded by a known molding method such as extrusion molding, or a method in which the olefin resin composition (α) is directly used as a filament during production, etc. For example, when the filament for three-dimensional shaping of the present invention is obtained by extrusion molding, the conditions are appropriately adjusted depending on the flow characteristics and moldability of the resin composition used, but are usually 150 to 300°C, preferably 170 to 250°C.

[0107] <Physical properties of filaments for 3D modeling> The diameter of the filament for three-dimensional modeling of the present invention depends on the specifications of the system used for molding a resin molded product by the fused deposition modeling method, but is usually 1.0 mm or more, preferably 1.5 mm or more, more preferably 1.6 mm or more, and particularly preferably 1.7 mm or more. On the other hand, the diameter of the filament for three-dimensional modeling of the present invention is usually 5.0 mm or less, preferably 4.0 mm or less, more preferably 3.5 mm or less, and particularly preferably 3.0 mm or less.

[0108] Furthermore, from the viewpoint of the stability of the supply of raw materials, it is preferable that the accuracy of the diameter is within an error of ±5% for any measurement point of the filament. In particular, the standard deviation of the diameter of the filament for three-dimensional modeling of the present invention is preferably 0.07 mm or less, and particularly preferably 0.06 mm or less.

[0109] In addition, the filament for three-dimensional shaping of the present invention preferably has a circularity of 0.93 or more, particularly preferably 0.95 or more. The upper limit of the circularity is 1.0. In this way, if the filament for three-dimensional shaping has a small standard deviation of diameter and a high circularity, uneven discharge during shaping can be suppressed, and a resin molded product having excellent appearance and surface properties can be stably produced. By using the above-mentioned olefin resin composition (α), a filament for three-dimensional shaping satisfying such standard deviation and circularity can be relatively easily produced.

[0110] <3D modeling filament winding body> When a resin molded body is manufactured by a three-dimensional printer using the filament for three-dimensional printing of the present invention, it is required to stably store the filament for three-dimensional printing and to stably supply the filament for three-dimensional printing to the three-dimensional printer. For this purpose, it is preferable that the filament for three-dimensional printing of the present invention is packaged as a wound body wound on a bobbin, or that the wound body is stored in a cartridge from the viewpoints of long-term storage, stable unwinding, protection from environmental factors such as ultraviolet rays, prevention of twisting, etc. As the cartridge, in addition to the wound body wound on a bobbin, a moisture-proof or moisture-absorbing material is used inside, and at least a structure other than an orifice part from which the filament is unwound is used, and a structure in which it is sealed is mentioned.

[0111] Typically, a bobbin containing filament for 3D modeling, or a cartridge containing the bobbin is placed inside or around the 3D printer, and filament is constantly being introduced from the cartridge into the 3D printer during modeling.

[0112] <Method of manufacturing resin molded body> In the method for producing a resin molded product of the present invention, the filament for three-dimensional modeling of the present invention is used to obtain a resin molded product by molding with a three-dimensional printer. Examples of molding methods using a three-dimensional printer include fused deposition modeling (ME method), powder sintering method, inkjet method, and stereolithography method (SLA method), but it is particularly preferable to use the filament for a three-dimensional printer of the present invention for fused deposition modeling. The following describes the case of fused deposition modeling as an example.

[0113] A three-dimensional printer generally has a chamber, and in the chamber, there are a heatable base, an extrusion head mounted on a gantry structure, a heat melter, a filament guide, a raw material supply unit such as a filament cartridge mounting unit, etc. Some three-dimensional printers have an extrusion head and a heat melter integrated together.

[0114] The extrusion head is installed in a gantry structure, so that it can be moved arbitrarily on the XY plane of the base. The base is a platform for constructing the desired three-dimensional object or support material, and is preferably designed to obtain adhesion with the laminate by heating and keeping warm, and to improve the dimensional stability of the resulting resin molded body as the desired three-dimensional object. In addition, in order to improve adhesion with the laminate, a sticky paste may be applied to the base, or a sheet or the like having good adhesion with the laminate may be attached. Examples of sheets having good adhesion with the laminate include sheets having fine irregularities on the surface, such as inorganic fiber sheets, and sheets made of the same type of resin as the laminate. Note that at least one of the extrusion head and the base is usually movable in the Z-axis direction perpendicular to the XY plane.

[0115] The number of extrusion heads is usually one to two. With two extrusion heads, two different polymers can be melted in different heads and selectively printed. In this case, one of the polymers can be a build material for building a 3D object, and the other can be a support material, which is required, for example, as a temporary fixture. This support material can then be removed, for example, by complete or partial dissolution in an aqueous system (for example, a basic or acidic medium).

[0116] The filament for 3D modeling is fed from the raw material supply section and fed to the extrusion head by a pair of opposing rollers or gears, where it is heated and melted, and extruded from the nozzle at the tip. The extrusion head moves in response to a signal sent based on the CAD model, supplying the raw material onto the substrate and depositing it in layers. After this process is completed, the layered deposit is removed from the substrate, and the support material is peeled off or excess parts are cut off as necessary to obtain a resin molded product as the desired 3D object.

[0117] Examples of means for continuously supplying raw material to the extrusion head include a method of feeding a filament or fiber, a method of feeding a powder or liquid from a tank or the like via a fixed amount feeder, a method of extruding pellets or granules plasticized with an extruder or the like, and feeding the same, etc. Among these, from the viewpoints of process simplicity and supply stability, the method of feeding a filament, i.e., the method of feeding the filament of the present invention described above, is most preferred.

[0118] When supplying a filament to a three-dimensional printer, it is common to engage the filament with a driving roll such as a nip roll or a gear roll, and supply it to the extrusion head while pulling it. In order to stabilize the supply of raw material by strengthening the gripping between the filament and the driving roll, it is also preferable to transfer a minute uneven shape to the surface of the filament, or to compound inorganic additives, spreaders, adhesives, rubbers, etc. to increase the friction resistance with the engagement part. If the filament has uneven thickness, it may not be possible to grip the filament by engaging with the driving roll, and the driving roll may spin idly, making it impossible to supply the filament to the extrusion head.

[0119] The filament for three-dimensional modeling of the present invention has a temperature of about 180 to 300° C. to obtain a flowability suitable for extrusion, which is a temperature that can be set in a typical three-dimensional printer. In the manufacturing method of the present invention, the temperature of the heated extrusion head is usually set to 290° C. or less, preferably 200 to 280° C., and the temperature of the base is usually set to 120° C. or less, so that a resin molded product can be stably manufactured.

[0120] The temperature of the molten resin discharged from the extrusion head (discharge temperature) is preferably 180°C or higher, more preferably 190°C or higher, and is preferably 300°C or lower, more preferably 290°C or lower, and even more preferably 280°C or lower. If the temperature of the molten resin is equal to or higher than the lower limit, it is preferable for extruding a resin with high heat resistance, and it is also preferable because it is possible to discharge the resin at high speed and the molding efficiency tends to improve. On the other hand, if the temperature of the molten resin is equal to or lower than the upper limit, it is easy to prevent the occurrence of defects such as thermal decomposition, burning, smoke, odor, and stickiness of the resin. In addition, if the temperature of the molten resin is equal to or lower than the upper limit, it is also preferable from the viewpoint of preventing the adhesion of thin pieces of the molten resin called stringiness and lumps of excess resin called lumps to the resin molded body, which deteriorates the appearance.

[0121] The molten resin is discharged from the extrusion head in the form of strands, preferably with a diameter of 0.01 to 1.0 mm, more preferably with a diameter of 0.02 to 0.5 mm. When the molten resin is discharged in such a shape, it is preferred because the reproducibility of the CAD model tends to be good.

[0122] High-speed modeling in the filament for three-dimensional modeling of the present invention means that the modeling speed is 1 mm / s or more. From the viewpoint of the time required for modeling, the modeling speed is preferably 3 mm / s or more, more preferably 5 mm / s or more, even more preferably 7 mm / s or more, and most preferably 10 mm / s or more. There is no particular upper limit, but the faster the better. However, in order to have a speed that does not cause problems in modeling such as the bending of the filament described above and the deterioration of the appearance described below, the modeling speed is preferably 100 mm / s or less, more preferably 80 mm / s or less, and even more preferably 60 mm / s or less.

[0123] When manufacturing a resin molded product using a 3D printer with a 3D modeling filament, when creating a molded product by stacking strand-shaped resin discharged from an extrusion head, unevenness (streaks, etc.) may occur on the surface of the molded product due to insufficient adhesion between the previously discharged strand of resin and the subsequent strand of resin discharged on top of it, or uneven discharge. If such unevenness exists on the surface of the molded product, not only will the appearance deteriorate, but the molded product may also be prone to breakage, and other problems may occur.

[0124] The filament for 3D modeling of the present invention has good adhesion between the previously extruded strand of resin and the subsequent strand of resin extruded on top of it, and also has a high elastic modulus around room temperature, making the filament less likely to bend; in other words, the high circularity of the diameter suppresses uneven extrusion during molding, and allows for the stable production of molded objects with excellent appearance and surface properties.

[0125] When making a molded product by stacking strand-like resin discharged from an extrusion head by a 3D printer, there is a process where the resin discharge is stopped and the nozzle is moved to the next lamination location. At this time, the resin does not break off and thin resin fibers are generated, which may remain on the surface of the molded product like strings. If strings like the above occur, it can cause problems such as a deterioration in the appearance of the molded product.

[0126] The filament for 3D modeling of the present invention has a high elastic modulus around room temperature, making it less likely to bend, i.e., it has a small standard deviation in diameter and high circularity. In addition, it has a moderate crystallization rate and high breaking strain, which suppresses stringiness and allows for the stable production of molded articles with excellent appearance and surface properties.

[0127] The resin molded product of the present invention may be heat-treated after shaping to promote or complete crystallization depending on the intended use.

[0128] In producing the resin molded article of the present invention, a support material may be molded at the same time. The type of support material is not particularly limited, but examples thereof include BVOH (butenediol vinyl alcohol), PVOH (polyvinyl alcohol), EVOH (ethylene-vinyl alcohol copolymer), and HIPS (high impact polystyrene).

[0129] (Applications of resin molded bodies) The resin molded article of the present invention is excellent in strength and heat resistance. Its applications are not particularly limited, and it can be suitably used for stationery, toys, covers for mobile phones and smartphones, parts such as grips, school teaching materials, repair parts for home appliances and office automation equipment, various parts for automobiles, motorcycles, bicycles, etc., materials for electrical and electronic equipment, agricultural materials, gardening materials, fishing materials, civil engineering and construction materials, medical supplies, etc. EXAMPLES

[0130] The present invention will be described in more detail with reference to the following examples, which are not to be construed as limiting the scope of the present invention. Various measurements and evaluations shown in the present specification were carried out as follows.

[0131] (1) Heat of crystallization (ΔHc) and crystallization temperature (Tc) Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., product name "Pyris1 DSC", in accordance with JIS K7122, approximately 10 mg of a sample was heated from 0°C to 250°C at a heating rate of 10°C / min, held at that temperature for 1 minute, and then cooled to 0°C at a cooling rate of 10°C / min. From the thermogram measured when this was done, the heat of crystallization (ΔHc) and crystallization temperature (Tc) (both during the cooling process) were calculated.

[0132] (2) Crystal melting temperature (Tm), glass transition temperature (Tg) Using a differential scanning calorimeter manufactured by PerkinElmer, Inc., model name "Pyris1 DSC", in accordance with JIS K7121, approximately 10 mg of the sample was heated from 0 °C to 250 °C at a heating rate of 10 °C / min, held at that temperature for 1 minute, then cooled to 0 °C at a cooling rate of 10 °C / min, and the crystal melting temperature (Tm) (°C) (during the second heating process) was determined from each thermogram measured when heating again to 250 °C at a heating rate of 10 °C / min.

[0133] (3) Storage modulus (E´) at 40 °C The filaments obtained in the examples and comparative examples were each formed into a sheet with a thickness of approximately 0.5 mm by hot pressing to obtain measurement samples. Using a dynamic viscoelasticity measuring machine (manufactured by A&D Company, Limited, model name: Viscoelastic Spectrometer DVA - 200), the storage modulus (E´) was measured from - 100 °C to 250 °C under the conditions of a vibration frequency of 10 Hz, a heating rate of 3 °C / min, and a strain of 0.1%, and the storage modulus (E´) at 40 °C was determined from the obtained data.

[0134] (4) Evaluation of the shaping of the three - dimensional printing filament <High - speed shaping property> Using a 3D printer (manufactured by Mutoh Industries, Ltd., model name: MF - 2200D), at a nozzle temperature of 220 °C, and with a PP tape (3M Scotch 315SN) attached to the shaping table, at a shaping table temperature of 70 °C, the behavior when shaping a dumbbell - shaped sample (length 75 mm, width 10 mm, thickness 5 mm) with the thickness direction of the sample as the Z - axis direction (lamination direction) was evaluated based on the following criteria.

[0135] 〇: When shaping at a shaping speed of 10 mm / s, the shaping could be completed without the filament bending during shaping. ×: When shaping at a shaping speed of 10 mm / s, filament bending occurred during the process (or from the beginning), and the shaping could not be completed.

[0136] <Z - axis strength, horizontal strength> In accordance with JIS K 7161, the maximum tensile strength (horizontal strength) and breaking elongation of a dumbbell-shaped sample (sample 1) produced for the evaluation of warpage during molding described below were measured. The maximum tensile strength (Z-axis strength) and breaking elongation of sample 2 below were measured. The value of Z-axis strength / horizontal strength was also calculated. Note that the larger the values ​​of horizontal strength and Z-axis strength, the more preferable. Also, the larger the value of breaking elongation, the more preferable. In particular, the closer Z-axis strength / horizontal strength is to 1, the better.

[0137] Sample 2 was prepared as follows. That is, a dumbbell-shaped sample (length 75 mm, width 10 mm, thickness 5 mm) was modeled using a 3D printer (manufactured by Muto Industries Ltd., product name: MF-2200D) with the length direction of the sample as the Z-axis direction (lamination direction). At that time, PP tape (3M Scotch 315SN) was attached to the modeling table, and sample 2 was produced under the modeling conditions of modeling table temperature 70°C, nozzle temperature 240°C, modeling speed 7 mm / s, and internal filling rate 100%.

[0138] <Interlayer adhesion> A tensile test was carried out on Sample 1 and Sample 2 above under conditions of an initial chuck distance of 45 mm, a speed of 50 mm / min, and 23° C., and the interlayer adhesion was evaluated based on the measured maximum tensile strength in accordance with the following criteria.

[0139] ○: Maximum tensile strength of sample 2 (Z-axis strength) / Maximum tensile strength of sample 1 (horizontal strength) ≧ 0.4 △: 0.4> Maximum tensile strength (Z-axis strength) of sample 2 / Maximum tensile strength (horizontal strength) of sample 1 ≧ 0.25 ×:0.25>Maximum tensile strength of sample 2 (Z-axis strength) / Maximum tensile strength of sample 1 (horizontal strength)

[0140] <Warping during molding> The evaluation sample (designated as Sample 1) was produced as follows. That is, a dumbbell-shaped sample (length 75 mm, width 10 mm, thickness 5 mm) was modeled using a 3D printer (manufactured by Muto Industries Ltd., product name: MF-2200D) with the thickness direction of the sample as the Z-axis direction (lamination direction). At that time, PP tape (3M Scotch 315SN) was attached to the modeling table, and the evaluation sample was manufactured under the modeling conditions of modeling table temperature 70°C, nozzle temperature 220°C, modeling speed 7 mm / s, and internal filling rate 100%.

[0141] After the evaluation sample was produced, it was removed from the modeling table and placed on a horizontal surface. The distances between the four corners of the evaluation sample and the horizontal surface were measured, and the average of the obtained values ​​was taken as the amount of warping. From this amount of warping, the warping during modeling was evaluated based on the following criteria. Note that, among the following criteria, the smaller the value of the amount of warping, the more preferable it is.

[0142] ◯: The amount of warping was less than 3 mm. ×: The amount of warping was 3 mm or more, or large warping occurred during printing, so printing could not be completed.

[0143] The raw materials used in the examples and comparative examples are listed below.

[0144] <Olefin-based resin composition (A)> (A-1); Japan Polypropylene Corporation, product name: Wellnex RMG02, Reactor TPO, Tm: 130°C, Tc: 86°C, ΔHc: 44 J / g, E´: 340 MPa, composition ratio (mass ratio): propylene / ethylene = 95 / 5 (A-2): Made by Japan Polypropylene Co., Ltd., product name: Wintec WMG03, propylene and ethylene random polymer, Tm: 142°C, Tc: 106°C, ΔHc: 80 J / g, E´: 1200 MPa, composition ratio (mass ratio): propylene / ethylene = 98 / 2

[0145] <Resin composition (B)> (B-1): manufactured by Mitsubishi Chemical Corporation, product name: Tefablock (registered trademark) MC931, Tg: 108°C, ΔHc: 5 J / g, composition: hydrogenated aromatic vinyl polymer block unit 60 mol%, hydrogenated conjugated diene polymer block unit 40 mol%, hydrogenation level: 99.5% or more, pentablock structure (B-2): Polyplastics Co., Ltd., product name: TOPAS (registered trademark) 5013L-10, Tg: 130°C, ΔHc: 0 J / g, composition: cycloolefin copolymer

[0146] Example 1 80 parts by mass of olefin resin (A-1) and 20 parts by mass of resin (B-1) were mixed and extruded from a nozzle with a diameter of 2.5 mm in a 20 mmφ co-rotating twin-screw kneader at a melt temperature of 200° C., and then cooled in cooling water at 30° C. to obtain a filament with a diameter of 1.75 mm. The various evaluation results of this filament are shown in Table 1.

[0147] Example 2 A filament was produced in the same manner as in Example 1, except that 60 parts by mass of the olefin resin composition (A-1) and 40 parts by mass of the resin composition (B-1) were blended in Example 1. Various evaluation results for this filament are shown in Table 1.

[0148] Example 3 A filament was produced in the same manner as in Example 2, except that the olefin resin composition (A-2) was used instead of the olefin resin composition (A-1) in Example 2. Various evaluation results for this filament are shown in Table 1.

[0149] Example 4 A filament was produced in the same manner as in Example 2, except that the resin (B-2) was used instead of the resin (B-1) in Example 2. Various evaluation results for this filament are shown in Table 1.

[0150] Comparative Example 1 A filament was produced in the same manner as in Example 1, except that the olefin resin composition was produced using only the olefin resin composition (A-1) in Example 1. Various evaluation results for this filament are shown in Table 1.

[0151] Comparative Example 2 A filament was produced in the same manner as in Example 1, except that the olefin resin composition was produced using only the olefin resin composition (A-2) in Example 1. Various evaluation results for this filament are shown in Table 1.

[0152] In addition, in the evaluation of warpage during modeling using the filament of Comparative Example 2, large warpage occurred during modeling, so modeling could not be completed to the end. Therefore, the evaluation of warpage during modeling was performed using a model in the middle of modeling. In addition, for the evaluation of horizontal strength, since a model suitable for a tensile test could not be obtained, a 0.5 mm thick sheet of hot-pressed filament was cut into 5 mm wide strips instead.

[0153] Comparative Example 3 Table 1 shows the results of various evaluations performed using a commercially available PP filament (Muto Industries Ltd., product name: Value3D MagiX material, PP, 1.75 mm).

[0154] The filament of Comparative Example 3 was heated from room temperature to 700°C in air at a heating rate of 20°C / min using a thermogravimetric analyzer (TGA Q5000IR, manufactured by TA Instruments Japan), and the amount of residue obtained and IR measurement of the residue were performed. From the results, it was determined that the filament of Comparative Example 3 contained 39% by mass of talc.

[0155] Furthermore, "24×ΔHc-E'" in Examples 1 to 4 and Comparative Examples 1 and 2 is a value for a filament made of at least one of the olefin resin composition (A) and the resin composition (B), while "24×ΔHc-E'" in Comparative Example 3 is a value for a filament containing talc. In other words, "24×ΔHc-E'" in Comparative Example 3 is different from the above formula [1].

[0156] [Table 1]

[0157] As can be seen from Table 1, the filaments of Examples 1 to 4 satisfy the above formula [1], and therefore are filaments that are excellent in formability, such as suppression of warping during forming, while maintaining high-speed formability.

[0158] Furthermore, the filaments of Examples 1 and 2 have interlayer adhesion equal to or greater than that of the filament made of the low-crystalline olefin resin composition (A) (Comparative Example 1), indicating that the resin composition (B-1) does not inhibit the interlayer adhesion.

[0159] Furthermore, a comparison between Example 2 and Example 4 shows that Example 2, which uses a resin composition (B-1) having a cyclic structure in the side chain, has higher Z-axis strength and interlayer adhesion than Example 4, which uses a resin composition (B-2) having a cyclic structure in the main chain.

[0160] In contrast, the filament of Comparative Example 1 has a low storage modulus measured at 40° C. and 10 Hz, and therefore the filament is easily bent and has poor high-speed modeling properties. On the other hand, the filament of Comparative Example 2 has a large ΔHc, and therefore warps significantly during molding, resulting in poor moldability. The filament of Comparative Example 3 exhibited high speed molding properties and warpage suppression effects, but had low interlayer adhesion, which is believed to be due to the talc inhibiting interlayer adhesion.

[0161] Although the present invention has been described in detail and with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2019-182009) filed on October 2, 2019, the contents of which are incorporated herein by reference.

Claims

1. The present invention comprises an olefin-based resin composition (α) which satisfies the following formula [1]: The olefin resin composition (α) contains a resin composition (B), The filament for three-dimensional modeling, wherein the resin composition (B) contains a cyclic olefin resin. 700≧24×ΔHc(α)−E′(α)...[1] ΔHc(α): the heat of crystallization (J / g) when the olefin resin composition (α) is measured with a differential scanning calorimeter at a temperature drop rate of 10° C. / min E'(α): storage modulus (MPa) of the olefin resin composition (α) measured at 40 ° C. and 10 Hz

2. The filament for three-dimensional shaping according to claim 1 , wherein the ΔHc (α) is 75 J / g or less.

3. The filament for three-dimensional shaping according to claim 1 or 2, wherein E'(α) is 350 MPa or more.

4. The olefin-based resin composition (α) contains an olefin-based resin composition (A), The resin composition (B) has a crystallization heat (ΔHc(B)) of less than 10 J / g when measured with a differential scanning calorimeter at a temperature drop rate of 10 ° C. / min. The filament for three-dimensional modeling according to any one of claims 1 to 3.

5. The filament for three-dimensional modeling according to claim 4, wherein the difference between the crystallization temperature of the olefin-based resin composition (A) measured at a temperature decrease rate of 10°C / min using a differential scanning calorimeter and the crystallization temperature of the olefin-based resin composition (α) measured at a temperature decrease rate of 10°C / min using a differential scanning calorimeter is 10°C or less.

6. The olefin-based resin composition (α) contains an olefin-based resin composition (A), The filament for three-dimensional modeling according to any one of claims 1 to 5, wherein the olefin-based resin composition (A) is at least one resin composition selected from the group consisting of a propylene homopolymer, a random copolymer of propylene with at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, a block copolymer of propylene with at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, a maleic anhydride grafted polypropylene, a blend of at least one of propylene and polyethylene with ethylene-propylene rubber, a dynamically crosslinked product of at least one of propylene and polyethylene with ethylene-propylene rubber, a polymer of at least one of propylene and polyethylene with ethylene-propylene rubber, a high-density polyethylene, a low-density polyethylene, and a linear low-density polyethylene.

7. The filament for three-dimensional modeling according to any one of claims 1 to 6, further comprising a filler.

8. A resin molded body containing a filament for three-dimensional modeling described in any one of claims 1 to 7.

9. A wound body of a filament for three-dimensional modeling described in any one of claims 1 to 7.

10. A cartridge for three-dimensional modeling containing a filament for three-dimensional modeling described in any one of claims 1 to 7.

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