JP7616059B2 - Filament for 3D modeling - Google Patents

Description

The present invention relates to a filament for three-dimensional modeling, a resin molded body, a wound body, and a cartridge for three-dimensional modeling.

Extrusion-based thermal layer deposition systems are what are 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 raw material from a nozzle on an extrusion head to build a three-dimensional object in layers based on a computer-aided design (CAD) model.

Among these, the fused deposition modeling (ME) method is a simple system in which a thermoplastic resin raw material is inserted as a filament into an extrusion head, and while being heated and melted, it is continuously extruded from a nozzle on the extrusion head onto an X-Y planar base in a chamber, and the extruded resin is deposited and fused onto an already deposited resin laminate, which solidifies as it cools. For this reason, 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 X-Y plane (Patent Documents 1 and 2).

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

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. For this reason, there is potential for a wide range of applications, including industrial applications such as modeling products and manufacturing tools.

However, such polyolefin resins are generally prone to crystallization. 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.

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

Japan Special Table No. 2003-502184 Japan Special Table Publication No. 2003-534159 Japan Special Table No. 2010-521339 Japanese Patent Application Publication No. 2008-194968 International Publication No. 2015/037574 Japanese Patent Application Publication No. 2017-197627

However, low-crystalline polyolefin resins such as those described in Patent Document 6 can suppress the occurrence of molding defects such as warping due to crystallization shrinkage during three-dimensional modeling, and can improve three-dimensional modeling properties. Furthermore, the modeling properties of polyolefin resins at relatively low speeds such as 0.5 mm/s have been improved.

However, as a result of the inventors' investigations, it became clear that the elastic modulus of low-crystalline polyolefin resins, particularly around room temperature, decreases as a result of low crystallinity, and therefore the strength of three-dimensionally molded resin moldings and the hardness of the filaments are insufficient. Therefore, the fields to which low-crystalline polyolefin resins such as those listed in Patent Document 6 can be applied are limited, and problems were 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 case of high-speed three-dimensional modeling of polyolefin resins, bending of the filament occurs, resulting in poor high-speed three-dimensional modeling properties.

Therefore, an object of the present invention is to provide a filament for 3D modeling that prevents warping of the model (resin molded body) during 3D modeling, and prevents bending of the filament even when the filament is sent to the extrusion head at high speed, such as in high-speed 3D modeling, resulting in good high-speed 3D modeling properties and excellent strength of the model (resin molded body). Another object of the present invention is to provide a resin molded body, a wound body, and a cartridge for 3D modeling that contain the filament for 3D modeling.

After extensive research, the inventors have concluded that the above problems can be solved by using a polyolefin resin composition having specific thermal properties and storage modulus.

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): 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 forming according to <1>, wherein the ΔHc (α) is 75 J/g or less.
<3> The filament for three-dimensional forming according to <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) and a resin composition (B),
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 <1> to <3>.
<5> The filament for three-dimensional modeling according to <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 printing according to any one of <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 olefin-based resin composition (α) contains a resin composition (B),
The filament for three-dimensional modeling according to any one of <1> to <6>, wherein the resin composition (B) contains a cyclic olefin resin.
<8> The filament for three-dimensional modeling according to any one of <1> to <7>, further comprising a filler.
<9> A resin molded product containing the filament for three-dimensional modeling according to any one of <1> to <8>.
<10> A wound body of the filament for three-dimensional modeling according to any one of <1> to <8>.
<11> A cartridge for three-dimensional modeling, comprising the filament for three-dimensional modeling according to any one of <1> to <8>.

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

[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. Therefore, the filament for three-dimensional modeling of the present invention has a small amount of crystallization shrinkage, and warping during three-dimensional modeling is suppressed.
In addition, the filament for three-dimensional modeling of the present invention has a high elastic modulus at around room temperature, so that the filament for three-dimensional modeling of the present invention can be prevented from bending during filament feeding.

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 to suppress warping, the modulus of elasticity near room temperature decreases and the filament becomes more prone to bending, making it difficult to simultaneously suppress warping during modeling and 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.

This effect can also be achieved, for example, by simply adding a filler to the filament. However, in this case, there is a concern that the filler will inhibit interlayer adhesion between the resin layers, reducing the strength (Z-axis strength) perpendicular to the layers of the model (resin molded body) when it is 3D modeled. On the other hand, the filament for 3D modeling of the present invention contains a specific resin, making it possible to achieve both a low amount of crystallization shrinkage and a high room temperature modulus while ensuring interlayer adhesion.

The following provides a detailed description of the form for implementing the present invention (hereinafter referred to as the "present embodiment"). The 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 implemented in various modifications within the scope of its gist.

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

<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.

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

Here, by having "24 x ΔHc(α) - E'(α)" be within the above range, warping during three-dimensional modeling is suppressed, and bending during filament feeding can also be suppressed.

In addition, the upper limit of "24 x 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.

In addition, from the viewpoint of achieving both high speed formability and interlayer adhesion, the lower limit of "24 x 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.

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 the molded object (resin molded body) due to crystallization shrinkage during three-dimensional modeling.

In addition, 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.

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

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, resulting in excellent moldability and excellent strength of the molded resin molding. 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.

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, which is preferable because it is easy to handle during modeling work (such as setting the filament in the printer).

In addition, 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.

The crystallization temperature (Tc(α)) of the olefin resin composition (α) when 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.

Furthermore, 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.

In addition, Tc(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.

The crystalline melting temperature (Tm(α)) of the olefin resin composition (α) measured with a differential scanning calorimeter at a heating rate of 10°C/min is not particularly limited, but from the viewpoint of ease of modeling with 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.

Furthermore, 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.

In addition, Tm(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.

The olefin resin composition (α) preferably contains an olefin resin composition (A) and a resin composition (B) described later. 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.

In addition, in this case, the difference between the crystallization temperature (Tc(A)) of the olefin-based resin composition (A) when measured at a temperature decrease rate of 10°C/min using a differential scanning calorimeter and the crystallization temperature (Tc(α)) of the olefin-based resin composition (α) when measured at a temperature decrease 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.

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

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

That is, examples of such copolymers include propylene homopolymers, random copolymers of propylene with at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, block copolymers of propylene with at least one monomer selected from ethylene and an α-olefin having 4 to 12 carbon atoms, maleic anhydride grafted polypropylene, blends of at least one of propylene and polyethylene with ethylene-propylene rubber, dynamically crosslinked products of at least one of propylene and polyethylene with ethylene-propylene rubber (thermoplastic vulcanizates), polymerization products 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.

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

The olefin-based resin composition (A) may consist of one resin selected from the above, or may consist of a combination of multiple resins selected from the above.

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.

In addition, 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.

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 the crystalline 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.

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 formability, 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.

Furthermore, 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.

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

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.

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

In addition, Tm(A) can be adjusted by the resin composition, stereoregularity, etc.

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 molding and the strength of the molded resin molding, 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.

In addition, from the standpoint of filament handleability, 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.

Furthermore, E'(A) can be adjusted by the resin composition, stereoregularity, etc.

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

In addition, the filament for three-dimensional modeling of the present invention may contain, in addition to the olefin-based resin composition (α), a filler, other resins, and other additives described below. In this case, the content of the olefin-based resin composition (α) in the filament for three-dimensional modeling 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, in terms of excellent heat resistance and modeling properties.

In addition, the content of the olefin-based resin composition (α) in the three-dimensional modeling filament 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.

In addition, when the olefin-based resin composition (α) contains the olefin-based resin composition (A) and the resin composition (B) described below, the content of the olefin-based resin composition (A) in the olefin-based 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.

In addition, from the viewpoint of formability, the content of olefin-based resin composition (A) in 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.

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

The lower limit of ΔHc(B) is not particularly limited, but is 0 J/g or more, and from the standpoint 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.

Specific examples of 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), etc.

Among them, cyclic olefin resins are preferred from the viewpoint of kneadability with the olefin resin composition (A). A cyclic olefin resin is an olefin resin having an alicyclic structure in the molecular chain. Examples of alicyclic structures include single ring structures such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane, and two ring structures such as norbornane, decalin, and spiropentane. These may be in the polymer main chain or in the side chain, but it is preferable that they are in the side chain in order to further improve kneadability and heat fusion with the olefin resin composition (A).

Examples of cyclic olefin resins include copolymers of ethylene and cyclic olefins (cycloalkenes), copolymers of α-olefins and cyclic olefins (cycloalkenes), ring-opening polymers of cyclic olefins (cycloalkenes), hydrogenated products of ring-opening polymers of cyclic olefins, and hydrogenated block copolymers which are hydrogenated products of block copolymers containing at least one type of aromatic vinyl monomer unit and at least one type of conjugated diene monomer unit.

Among these, from the viewpoint of kneadability and heat fusion with the olefin resin composition (A), 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, is preferred as a resin having an alicyclic structure in a side chain. Furthermore, 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.

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 of the hydrogenated aromatic vinyl polymer block units and at least one of the hydrogenated conjugated diene polymer block units.

In this specification, the term "block" refers to a polymerization segment of a copolymer 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" means that the hydrogenated block copolymer has at least two polymerization segments of a copolymer that exhibit microphase separation from structurally or compositionally distinct polymerization segments.

The aromatic vinyl monomer used as the raw material for the aromatic vinyl monomer unit is a monomer represented by the following general formula (1):

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.

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 alkyl group preferably has 1 to 6 carbon atoms. The Ar is preferably a phenyl group or an alkylphenyl group, and more preferably a phenyl group.

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.

The conjugated diene monomer used 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.

Examples of conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3-pentadiene and similar compounds, and mixtures thereof.

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

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 without functional groups. Note that "without 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.

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 groups or structural modifiers.

"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.

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

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, relative to 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, relative to the cyclic polyolefin.

If the ratio of hydrogenated aromatic vinyl polymer block units is equal to or greater than the above lower limit, rigidity will not decrease, and if it is equal to or less than the above upper limit, brittleness will not worsen.

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. 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.

If the ratio of hydrogenated conjugated diene polymer block units is equal to or greater than the above lower limit, brittleness will not worsen, and if it is equal to or less than the above upper limit, rigidity will not decrease, resulting in excellent strength of the molded resin molding.

The hydrogenated block copolymers are produced 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).

The hydrogenated block copolymer contains a segment of aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units. And, between these two hydrogenated aromatic vinyl polymer block units, there is at least one hydrogenated conjugated diene polymer block unit.

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, with the polymer chains attached at any position along the backbone of the copolymer.

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.

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).

The hydrogenation level of the block copolymer is preferably 90% or more of hydrogenated aromatic vinyl polymer block units and 95% or more of hydrogenated conjugated diene polymer block units, more preferably 95% or more of hydrogenated aromatic vinyl polymer block units and 99% or more of hydrogenated conjugated diene polymer block units, even more preferably 98% or more of hydrogenated aromatic vinyl polymer block units and 99.5% or more of hydrogenated conjugated diene polymer block units, and particularly preferably 99.5% or more of hydrogenated aromatic vinyl polymer block units and 99.5% or more of hydrogenated conjugated diene polymer block units.

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

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

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 body formed using it, it is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, particularly preferably 90°C or higher, and most preferably 100°C or higher. In addition, from the viewpoint of kneadability with the olefin-based resin composition (A) and moldability (suppression of warping during molding), the glass transition temperature (Tg) of the resin composition (B) is preferably 200°C or lower, more preferably 180°C or lower, even more preferably 160°C or lower, particularly preferably 150°C or lower, and most preferably 140°C or lower.

Here, the glass transition temperature (Tg) is the value measured using a differential scanning calorimeter (DSC) in accordance with JIS K7121 when approximately 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.

From the viewpoint of heat resistance, 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 formability, 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.

<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.

In addition to the olefin-based resin composition (α), the filament for three-dimensional modeling of the present invention may contain fillers (such as organic particles, inorganic particles, and reinforcing materials), other resins, and other components to an extent that does not impair the effects of the present invention.

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, UV absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slip agents, crystal nucleating agents, tackifiers, sealability improvers, anti-fogging agents, release agents, plasticizers, pigments, dyes, fragrances, flame retardants, etc.

Here, specific examples of organic particles among the fillers include acrylic resin particles, melamine resin particles, silicone resin particles, polystyrene resin particles, etc.

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

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.

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

Here, the content of the filler is not particularly specified, but from the viewpoint of the strength of the resin molded body 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, relative to 100% by mass of the resin composition (α). Also, from the viewpoint of suppressing a decrease in interlayer adhesion of the resin molded body 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.

<Method of manufacturing filament for 3D modeling>
The filament for three-dimensional modeling 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.

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

The method for producing the filament for three-dimensional modeling 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. For example, when the filament for three-dimensional modeling 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.

<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.

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.

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

<Wound body of filament for 3D modeling>
When a resin molded body is manufactured by a three-dimensional printer using the filament for three-dimensional modeling of the present invention, it is required to stably store the filament for three-dimensional modeling and stably supply the filament for three-dimensional modeling to the three-dimensional printer. For this purpose, it is preferable that the filament for three-dimensional modeling of the present invention is packaged as a wound body wound around 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. Examples of the cartridge include a wound body wound around a bobbin, and a cartridge having a structure in which a moisture-proof material or moisture-absorbing material is used inside and at least the part other than the orifice part from which the filament is unwound is sealed.

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 into the 3D printer from the cartridge during modeling.

<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.

Three-dimensional printers generally have a chamber that contains a heatable base, an extrusion head mounted on a gantry structure, a heat melter, a filament guide, a filament cartridge mounting section, and other raw material supply sections. Some three-dimensional printers have an integrated extrusion head and heat melter.

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 be capable of obtaining adhesion with the laminate by heating and keeping it warm, and improving 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 that has good adhesion with the laminate may be attached. Examples of sheets that have good adhesion with the laminate include sheets with 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.

The number of extrusion heads is usually one or two. With two extrusion heads, two different polymers can be melted in different heads and printed selectively. In this case, one of the polymers can be a build material for building the 3D object, while the other can be a support material, which is needed, 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).

The filament for 3D modeling is unwound 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. In response to a signal sent based on the CAD model, the extrusion head moves to its position, supplying raw material onto the base and depositing it in layers. After this process is completed, the layered deposit can be removed from the base, and supporting materials can be peeled off or excess parts cut off as necessary to obtain a resin molded product as the desired 3D object.

Examples of means for continuously supplying raw material to the extrusion head include a method of unwinding and supplying filaments or fibers, a method of supplying 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 the like. Among these, from the standpoint of process simplicity and supply stability, the method of unwinding and supplying filaments, i.e., the method of unwinding and supplying the filaments for three-dimensional modeling of the present invention described above, is the most preferred.

When supplying filament to a 3D printer, it is common to engage the filament with a driving roll such as a nip roll or gear roll, and supply it to the extrusion head while pulling it. In order to stabilize the supply of raw material by strengthening the grip of the filament by the engagement of 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 frictional resistance with the engagement part. If the filament has uneven thickness, it may not be possible to grip the filament by the engagement of the driving roll, causing the driving roll to spin freely and making it impossible to supply the filament to the extrusion head.

The temperature of the filament for three-dimensional modeling of the present invention to obtain the appropriate fluidity for extrusion is usually about 180 to 300°C, 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 290°C or less, preferably 200 to 280°C, and the base temperature is usually 120°C or less, allowing stable production of resin molded products.

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 more 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 above lower limit, it is preferable for extruding a resin with high heat resistance, and it is also preferable because it is possible to discharge 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 above 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 above upper limit, it is also preferable from the viewpoint of preventing the adhesion of thin pieces of molten resin called stringing and lumps of excess resin called lumps to the resin molded body, which deteriorates the appearance.

The molten resin is extruded 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 extruded in such a shape, it is preferred because it tends to result in good reproducibility of the CAD model.

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 ensure that the speed does not cause problems in modeling, such as the bending of the filament described above or 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.

When manufacturing resin molded products with a 3D printer using 3D modeling filaments, as the molded product is made by stacking strands of resin extruded from the extrusion head, unevenness (streaks, etc.) can occur on the surface of the molded product due to insufficient adhesion between the previously extruded strand of resin and the strand of resin extruded on top of it, or uneven extrusion. The presence of such unevenness on the surface of the molded product not only deteriorates the appearance, but can also cause problems such as the molded product being more susceptible to breakage.

The filament for three-dimensional modeling of the present invention has good adhesion between the previously extruded strand of resin and the strand of resin extruded on top of it, and also has a high elastic modulus near room temperature, making the filament less likely to bend; in other words, the high circularity of the diameter suppresses uneven extrusion during molding, allowing for the stable production of molded products with excellent appearance and surface properties.

When creating a molded product by stacking strands of resin extruded from an extrusion head using a 3D printer, there is a process in which the resin extrusion 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 produced, which sometimes remain on the surface of the molded product like strings. When strings like this occur, it can cause problems such as a deterioration in the appearance of the molded product.

The filament for three-dimensional modeling of the present invention has a high elastic modulus near room temperature and is less likely to bend, i.e., 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 products with excellent appearance and surface properties.

Depending on the intended use, etc., the resin molded body of the present invention may be heat-treated after molding to promote or complete crystallization.

When 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 include BVOH (butenediol vinyl alcohol), PVOH (polyvinyl alcohol), EVOH (ethylene-vinyl alcohol copolymer), and HIPS (high impact polystyrene).

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

The following examples are provided in further detail, but the present invention is not limited by them. The various measurements and evaluations shown in this specification were performed as follows.

(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, about 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 heating 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 determined.

(2) Crystal melting temperature (Tm), glass transition temperature (Tg)
Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., product name "Pyris1 DSC", in accordance with JIS K7121, about 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, cooled to 0°C at a heating rate of 10°C/min, and then heated again to 250°C at a heating rate of 10°C/min. From the thermograms measured at these times, the crystalline melting temperature (Tm) (°C) (reheating process) was determined.

(3) Storage modulus at 40° C. (E′)
The filaments obtained in the examples and comparative examples were each molded into a sheet having a thickness of about 0.5 mm by heat pressing to prepare a measurement sample. The storage modulus (E') was measured from -100°C to 250°C under the conditions of vibration frequency: 10 Hz, heating rate: 3°C/min, and strain: 0.1% using a dynamic viscoelasticity measuring device (IT Measurement Co., Ltd., product name: Viscoelasticity Spectrometer DVA-200), and the storage modulus (E') at 40°C was calculated from the obtained data.

(4) Evaluation of filament for 3D modeling <High-speed modeling ability>
Using a 3D printer (manufactured by Muto Industries Ltd., product name: MF-2200D), with a nozzle temperature of 220°C and PP tape (3M Scotch 315SN) attached to the modeling table, and a modeling table temperature of 70°C, a dumbbell-shaped sample (length 75 mm, width 10 mm, thickness 5 mm) was modeled with the thickness direction of the sample in the Z-axis direction (stacking direction). The behavior of the sample when modeled was evaluated based on the following criteria.

A: When modeling was performed at a modeling speed of 10 mm/s, the filament was not bent during modeling and the modeling could be completed.
×: When modeling was performed at a modeling speed of 10 mm/s, bending of the filament occurred during (or from the beginning) the modeling could not be completed.

<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) prepared for the evaluation of warpage during molding described below were measured. The strength (Z-axis strength) and breaking elongation were measured. The value of Z-axis strength/horizontal strength was also calculated. Note that the larger the horizontal strength and Z-axis strength values, the more preferable they are. For the same reason, the larger the value, the more preferable it is. In particular, the closer the Z-axis intensity/horizontal intensity is to 1, the better.

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 manufactured under modeling conditions of a modeling table temperature of 70°C, a nozzle temperature of 240°C, a modeling speed of 7 mm/s, and an internal filling rate of 100%.

<Interlayer Adhesion>
A tensile test was carried out on Sample 1 and Sample 2 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.

◯: Maximum tensile strength (Z-axis strength) of sample 2 / maximum tensile strength (horizontal strength) of sample 1 ≧0.4
Δ: 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 (Z-axis strength) of sample 2/maximum tensile strength (horizontal strength) of sample 1

<Warping during modeling>
The evaluation sample (designated Sample 1) 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 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 modeling conditions of a modeling table temperature of 70°C, a nozzle temperature of 220°C, a modeling speed of 7 mm/s, and an internal filling rate of 100%.

After producing the evaluation sample, the evaluation sample was removed from the modeling table and placed on a horizontal surface. The distance between the four corners of the evaluation sample and the horizontal surface was 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 even within the following criteria, the smaller the amount of warping, the more preferable it is.

A: The amount of warping was less than 3 mm.
×: The amount of warping was 3 mm or more, or a large warping occurred during the molding process, so that the molding could not be completed.

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

<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): Manufactured by Japan Polypropylene Corporation, product name: Wintec WMG03, random polymer of propylene and ethylene, Tm: 142°C, Tc: 106°C, ΔHc: 80 J/g, E': 1200 MPa, composition ratio (mass ratio): propylene/ethylene = 98/2

<Resin composition (B)>
(B-1): 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 %, hydrogen 40 mol% hydrogenated conjugated diene polymer block unit, hydrogenation level: 99.5% or more, pentablock structure (B-2); manufactured by Polyplastics Co., Ltd., product name: TOPAS (registered trademark) 5013L-10, Tg : 130°C, ΔHc: 0 J/g, composition: cycloolefin copolymer

Example 1
80 parts by mass of olefin resin (A-1) and 20 parts by mass of resin (B-1) were blended, extruded from a nozzle having 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 having a diameter of 1.75 mm. Various evaluation results for this filament are shown in Table 1.

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.

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. The results of various evaluations of this filament are shown in Table 1.

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. The results of various evaluations of this filament are shown in Table 1.

(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.

(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.

In addition, in the evaluation of warping during modeling using the filament of Comparative Example 2, significant warping occurred during modeling, and modeling could not be completed to the end. Therefore, the evaluation of warping during modeling was performed using a model that was in the middle of being modeled. In addition, for the evaluation of horizontal strength, since it was not possible to obtain a model that could be subjected to a tensile test, a 0.5 mm thick sheet of hot-pressed filament cut into 5 mm wide strips was used instead.

(Comparative Example 3)
Various evaluation results were performed using a commercially available PP filament (manufactured by Muto Industries Ltd., product name: Value3D MagiX material, PP, 1.75 mm), and the results are shown in Table 1.

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.

In addition, "24 x 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-based resin composition (A) and the resin composition (B), while "24 x ΔHc-E'" in Comparative Example 3 is a value for a filament containing talc. In other words, "24 x ΔHc-E'" in Comparative Example 3 is different from the above formula [1].

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

Furthermore, the filaments of Examples 1 and 2 exhibited interlayer adhesion equal to or greater than that of the filament made of a low-crystalline olefin-based resin composition (A) (Comparative Example 1), indicating that the resin composition (B-1) did not inhibit interlayer adhesion.

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.

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.

Although the present invention has been described in detail and with reference to specific embodiments, it will be 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 (10)

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 The filament for three-dimensional modeling according to claim 1, wherein the ΔHc(α) is 75 J/g or less. The filament for three-dimensional modeling according to claim 1 or 2, wherein E'(α) is 350 MPa or more. The olefin resin composition (α) contains an olefin 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. 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 with a differential scanning calorimeter at a temperature drop rate of 10°C/min and the crystallization temperature of the olefin-based resin composition (α) measured with a differential scanning calorimeter at a temperature drop rate of 10°C/min is 10°C or less. 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. The filament for three-dimensional modeling according to any one of claims 1 to 6 , further comprising a filler. A resin molded product comprising the filament for three-dimensional modeling according to any one of claims 1 to 7 . A wound body of the filament for three-dimensional modeling according to any one of claims 1 to 7 . A cartridge for three-dimensional modeling, comprising the filament for three-dimensional modeling according to any one of claims 1 to 7 .