WO2021066102A1 - Filament for three-dimensional printing - Google Patents

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

Filament for 3D modeling

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

The Fused Deposition Modeling System by Extrusion is a system generally called a 3D printer (3D printer) today, and examples thereof include a Fused Deposition Modeling System manufactured by Stratasys Incorporated in the United States. Fused Deposition Modeling Systems by Extrusion are used to extrude a fluid raw material from a nozzle site on an extrusion head to build a three-dimensional object in layers based on a computer-aided design (CAD) model.

Among them, the Fused Deposition Modeling method (ME method) inserts a raw material made of a thermoplastic resin into an extrusion head as a filament, and continuously heats and melts the material from the nozzle portion provided on the extrusion head onto the XY plane substrate in the chamber. It is a simple system in which the extruded resin is deposited and fused on a resin laminate that has already been deposited, and this is integrally solidified as it cools. Therefore, the ME method has come to be widely used. In the ME method, a three-dimensional object similar to a CAD model is usually constructed by repeating an extrusion process while the nozzle position with respect to the substrate rises in the Z-axis direction perpendicular to the XY plane (Patent Document 1, Patent Document 1, 2).

Conventionally, as a raw material for the ME method, an amorphous or hard-to-crystallize thermoplastic resin such as an acrylonitrile-butadiene-styrene resin or polylactic acid is generally preferable from the viewpoint of molding processability and fluidity. It has been used (Patent Documents 3 to 5).

On the other hand, in recent years, not only the above-mentioned plastics but also crystalline resins such as polypropylene-based resins have been studied for use as ME-type three-dimensional modeling materials. These are excellent in heat resistance, chemical resistance, strength and the like. Therefore, it may be widely used for industrial purposes such as modeling of products and manufacturing tools.

However, such polyolefin resins are generally easy to crystallize. Therefore, in the ME method three-dimensional molding using a polyolefin resin, the adhesiveness between the layers in the molded product is lowered, and the molded product (resin molded product) is warped due to crystallization shrinkage. Lowness was a problem.

On the other hand, a three-dimensional modeling material using a low crystallinity polyolefin resin is disclosed (Patent Document 6).

Japan Special Table 2003-502184 Japan Special Table 2003-534159 Japan Special Table 2010-521339 Gazette Japanese Patent Application Laid-Open No. 2008-194966 International Publication No. 2015/037574 Japanese Patent Application Laid-Open No. 2017-197627

However, the low crystallinity polyolefin resin as described in Patent Document 6 can suppress the occurrence of molding defects such as warpage due to crystallization shrinkage during three-dimensional modeling, and can improve the three-dimensional formability. is there. Further, the formability of the polyolefin resin at a relatively low speed such as 0.5 mm / s can be improved.

However, as a result of the studies by the present inventors, the low crystallinity of the low crystallinity polyolefin resin lowers the elastic modulus especially near room temperature, so that the strength of the three-dimensionally molded resin molded product and the filament It became clear that the hardness was not sufficient. Therefore, the fields to which the low crystallinity polyolefin resin as mentioned in Patent Document 6 can be applied are limited, and a problem has been found when the molding speed is increased in order to improve the productivity. .. Specifically, when the filament is sent to the extrusion head at high speed, as in the case of high-speed 3D modeling of polyolefin resin, a new problem is clarified that the filament bends and the high-speed 3D formability becomes poor. became.

Therefore, an object of the present invention is to bend the filament even when the filament is sent to the extrusion head at high speed, such as warpage of a modeled object (resin molded body) during three-dimensional modeling or high-speed three-dimensional modeling. It is an object of the present invention to provide a filament for three-dimensional modeling, which does not cause a problem, has good high-speed three-dimensional formability, and has excellent strength of a modeled object (resin molded body). Another object of the present invention is to provide a resin molded body, a wound body, and a three-dimensional modeling cartridge containing the three-dimensional modeling filament.

As a result of diligent studies, the present inventors have considered that the above-mentioned problems can be solved by using a polyolefin-based resin composition having a specific thermal property and storage elastic modulus.

That is, the gist of the present invention is as follows.
<1> A filament for three-dimensional modeling containing an olefin resin composition (α) satisfying the following formula [1].
700 ≧ 24 × ΔHc (α) -E'(α) ... [1]
ΔHc (α): The amount of heat of crystallization (J / g) when the olefin resin composition (α) was measured with a differential scanning calorimeter at a temperature lowering rate of 10 ° C./min.
E'(α): Storage elastic modulus (MPa) of the olefin resin composition (α) measured at 40 ° C. and 10 Hz.
<2> The three-dimensional modeling filament according to <1>, wherein the ΔHc (α) is 75 J / g or less.
<3> The three-dimensional modeling filament according to <1> or <2>, wherein the E'(α) is 350 MPa or more.
<4> The olefin-based resin composition (α) contains the olefin-based resin composition (A) and the resin composition (B).
The resin composition (B) has a crystallization calorific value (ΔHc (B)) of less than 10 J / g when measured at a temperature lowering rate of 10 ° C./min with a differential scanning calorimeter, <1> to <3. > The filament for three-dimensional modeling according to any one of.
<5> The crystallization temperature when measured at a temperature decrease rate of 10 ° C./min with the differential scanning calorimeter of the olefin resin composition (A) and the differential scanning calorimetry of the olefin resin composition (α). The three-dimensional molding filament according to <4>, wherein the difference from the crystallization temperature when measured at a temperature lowering rate of 10 ° C./min is 10 ° C. or less.
<6> The olefin-based resin composition (α) contains the olefin-based resin composition (A).
The olefin resin composition (A) is a propylene homopolymer, a random copolymer of ethylene and at least one monomer of α-olefin having 4 to 12 carbon atoms and propylene, ethylene and α having 4 to 12 carbon atoms. -A block copolymer of at least one monomer of olefin and propylene, a blend of at least one maleic anhydride graft polypropylene, propylene and polyethylene and ethylene-propylene rubber, and at least one of propylene and polyethylene and ethylene-propylene rubber. A dynamically crosslinked product, a polymer of at least one of propylene and polyethylene and an ethylene-propylene rubber, at least one resin composition selected from the group consisting of high density polyethylene, low density polyethylene, and linear low density polyethylene. The filament for three-dimensional modeling according to any one of <1> to <5>.
<7> The olefin-based resin composition (α) contains the resin composition (B).
The three-dimensional modeling filament 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>, which further contains a filler.
<9> A resin molded product containing the three-dimensional molding filament according to any one of <1> to <8>.
<10> The wound body of the three-dimensional modeling filament according to any one of <1> to <8>.
<11> A three-dimensional modeling cartridge containing the three-dimensional modeling filament according to any one of <1> to <8>.

According to the present invention, the filament does not bend even when the filament is sent to the extrusion head at high speed, as in the case of warpage of a modeled object (resin molded product) during 3D modeling or high-speed 3D modeling, and high speed 3 It is possible to provide a polyolefin-based three-dimensional molding filament having good dimensional moldability and excellent strength of a molded product (resin molded product). Further, according to the present invention, it is possible to provide a resin molded body, a wound body, and a three-dimensional modeling cartridge containing the three-dimensional modeling filament.

[Reason for the effect of the invention]
The reason why the present invention will be effective is not yet clear, but it can be inferred that the reason is as follows.
That is, the three-dimensional modeling filament of the present invention has a low amount of heat of crystallization. Therefore, the filament for three-dimensional modeling of the present invention has a small amount of crystallization shrinkage, and warpage during three-dimensional modeling is suppressed.
Further, the filament for three-dimensional modeling of the present invention has a high elastic modulus near room temperature. Therefore, the three-dimensional modeling filament of the present invention can also suppress bending during filament feeding.

In general polyolefin resins, the calorific value of crystallization and the elastic modulus near room temperature are in a proportional relationship. Therefore, if the calorific value of crystallization is lowered in order to suppress warpage, the elastic modulus near room temperature decreases and the filament easily bends. It is difficult to suppress warpage and filament bending at the same time during molding. However, the filament for three-dimensional modeling of the present invention can simultaneously suppress warpage and bending by containing a specific resin.

Further, such an effect can be obtained by simply adding a filler or the like to the filament, for example. However, in this case, there is a concern that the filler inhibits the interlayer adhesion between the resins and reduces the strength (Z-axis strength) of the modeled product (resin molded product) in the vertical direction with respect to the interlayer when the resin is three-dimensionally molded. On the other hand, the filament for three-dimensional modeling of the present invention can achieve both a low amount of crystallization shrinkage and a high room temperature elastic modulus while ensuring interlayer adhesiveness by containing a specific resin.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with various modifications within the scope of the gist thereof.

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

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

700 ≧ 24 × ΔHc (α) -E'(α) ... [1]
ΔHc (α): The amount of heat of crystallization (J / g) when the olefin resin composition (α) was measured with a differential scanning calorimeter at a temperature lowering rate of 10 ° C./min.
E'(α): Storage elastic modulus (MPa) of the olefin resin composition (α) measured at 40 ° C. and 10 Hz.

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

The upper limit of "24 x ΔHc (α) -E'(α)" is not particularly limited, but is preferably 500 or less, preferably 300 or less, from the viewpoint of achieving both high-speed formability and interlayer adhesion. More preferably, it is more preferably 100 or less, particularly preferably 0 or less, still more preferably -100 or less, and most preferably -200 or less.

Further, the lower limit of "24 x ΔHc (α) -E'(α)" is preferably −2000 or more, and more preferably -1500 or more, from the viewpoint of achieving both high-speed formability and interlayer adhesion. It is preferably −1000 or more, more preferably −500 or higher, and most preferably −300 or higher.

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, still more preferably 50 J / g or less. , 45 J / g or less, more preferably 40 J / g or less, and most preferably 30 J / g or less. As a result, it is possible to reduce the warp of the modeled product (resin molded product) due to crystallization shrinkage during three-dimensional modeling.

Further, ΔHc (α) is preferably 1 J / g or more, more preferably 5 J / g or more, further preferably 8 J / g or more, particularly preferably 10 J / g or more, and 15 J / g or more from the viewpoint of heat resistance. Most preferred.

Further, ΔHc (α) can be adjusted by the composition of the resin, the blend ratio of the olefin resin composition (A) and the resin composition (B) described later, and the like.

E'(α) is not particularly limited, but is usually 350 MPa or more. When E'(α) is within this range, bending during filament feeding is suppressed, the formability is excellent, and the strength of the molded resin molded body is excellent. E'(α) is preferably 400 MPa or more, more preferably 500 MPa or more, further preferably 800 MPa or more, particularly preferably 1000 MPa or more, and most preferably 1200 MPa or more.

The upper limit of E'(α) is not particularly limited, but E'(α) is preferably 5000 MPa or less, more preferably 4500 MPa or less, further preferably 4000 MPa or less, particularly preferably 3500 MPa or less, and 3000 MPa or less. It is more preferable, and 2500 MPa or less is most preferable. When E'(α) is within this range, the hardness of the filament becomes appropriate, and handling during modeling work (setting of the filament to the printer, etc.) is easy, which is preferable.

Further, E'(α) can be adjusted by the composition of the resin, the blend ratio of the olefin resin composition (A) and the resin composition (B) described later, and the like.

The crystallization temperature (Tc (α)) of the olefin resin composition (α) when measured at a temperature lowering rate of 10 ° C./min with a differential scanning calorimeter is not particularly limited, but at the time of modeling. From the viewpoint of suppressing warpage, it is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, further preferably 120 ° C. or lower, particularly preferably 110 ° C. or lower, and 100 ° C. or lower. Is the most preferable.

Further, from the viewpoint of heat resistance, Tc (α) is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher.

Further, Tc (α) can be adjusted by the composition of the resin, the blend ratio of the olefin resin composition (A) and the resin composition (B) described later, and the like.

The crystal melting temperature (Tm (α)) of the olefin resin composition (α) when measured at a heating rate of 10 ° C./min with a differential scanning calorimeter is not particularly limited, but is general-purpose. From the viewpoint of easy modeling with a three-dimensional printer, the temperature is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, further preferably 200 ° C. or lower, particularly preferably 150 ° C. or lower, and 140 ° C. Most preferably:

Further, from the viewpoint of heat resistance, Tm (α) is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, further preferably 60 ° C. or higher, particularly preferably 80 ° C. or higher, and most preferably 100 ° C. or higher.

Further, Tm (α) can be adjusted by the composition of the resin, the blend ratio of the olefin resin composition (A) and the resin composition (B) described later, and the like.

The olefin-based resin composition (α) preferably contains the olefin-based resin composition (A) described later and the resin composition (B). The resin composition (B) has a crystallization heat quantity (ΔHc (B)) of less than 10 J / g when measured with a differential scanning calorimeter at a temperature lowering rate of 10 ° C./min.

At this time, the crystallization temperature (Tc (A)) of the olefin resin composition (A) when measured at a temperature lowering rate of 10 ° C./min with a differential scanning calorimeter and the olefin resin composition (Tc (A)) and the olefin resin composition ( The difference between α) and the crystallization temperature (Tc (α)) measured at a temperature lowering rate of 10 ° C./min with a differential scanning calorimeter is not particularly limited, but is 10 ° C. or less. It is preferably 8 ° C. or lower, more preferably 6 ° C. or lower, particularly preferably 4 ° C. or lower, and most preferably 2 ° C. or lower.

That is, it is preferable that the crystallization of the olefin resin composition (A) is not easily inhibited by the resin composition (B). As a result, the heat resistance of the resin molded product formed by the three-dimensional molding filament of the present invention is excellent.

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

That is, a propylene homopolymer, a random copolymer of ethylene and at least one monomer of α-olefin having 4 to 12 carbon atoms and propylene, and at least one monomer of ethylene and α-olefin having 4 to 12 carbon atoms and propylene. Block copolymer with, blend of at least one of propylene and polyethylene and ethylene-propylene rubber, dynamically crosslinked product of at least one of propylene and polyethylene and ethylene-propylene rubber (Themoplastic Vulcanizates), Examples thereof include a polymer product of at least one of propylene and polyethylene and ethylene-propylene rubber (reactor TPO), high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE).

Among these, from the viewpoint of heat resistance, a propylene homopolymer, a random copolymer of ethylene and at least one monomer of an α-olefin having 4 to 12 carbon atoms and propylene, and an α-olefin having ethylene and 4 to 12 carbon atoms. Block copolymer of at least one monomer and propylene, dynamic cross-linked product of at least one of propylene and polyethylene and ethylene-propylene rubber (Themoplastic Vulcanizates), polymerization of at least one of propylene and polyethylene and ethylene-propylene rubber The product (reactor TPO) is preferable.

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

The calorific value for crystallization (ΔHc (A)) measured by the differential scanning calorimeter of the olefin resin composition (A) at a temperature lowering rate of 10 ° C./min is not particularly limited, but from the viewpoint of formability. Therefore, 120 J / g or less is preferable, 110 J / g or less is more preferable, 100 J / g or less is further preferable, 85 J / g or less is particularly preferable, and 70 J / g or less is most preferable.

Further, ΔHc (A) is preferably 10 J / g or more, more preferably 20 J / g or more, further preferably 30 J / g or more, particularly preferably 40 J / g or more, and particularly preferably 50 J / g or more, from the viewpoint of heat resistance. Most preferred.

Here, the crystallization calorie (ΔHc) in the present invention is a crystal melting temperature (Tm) from room temperature at a heating rate of 10 ° C./min for about 10 mg of a sample according to JIS K7122 using a differential scanning calorimeter (DSC). It is a value measured when the temperature is raised to + 20 ° C. or higher, held at the temperature for 1 minute, and then lowered to 0 ° C. at a temperature lowering rate of 10 ° C./min.

The crystallization temperature (Tc (A)) measured by the differential scanning calorimeter of the olefin resin composition (A) at a temperature lowering rate of 10 ° C./min is not particularly limited, but is 150 ° C. from the viewpoint of formability. The temperature is preferably 140 ° C. or lower, more preferably 130 ° C. or lower, particularly preferably 120 ° C. or lower, and most preferably 110 ° C. or lower.

Further, from the viewpoint of heat resistance, Tc (A) is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and more preferably 80 ° C. or higher. It is particularly preferable, and most preferably 90 ° C. or higher.

Further, Tc (A) can be adjusted by the composition of the resin and the stereoregularity.

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

The upper limit of Tm (A) is not particularly limited, and Tm (A) is generally preferably 200 ° C. or lower, more preferably 195 ° C. or lower, further preferably 190 ° C. or lower, and particularly preferably 185 ° C. or lower. It is preferably 180 ° C. or lower.

Further, Tm (A) can be adjusted by the composition of the resin, the stereoregularity, and the like.

The storage elastic modulus (E'(A)) of the olefin resin composition (A) measured at 40 ° C. and 10 Hz is not particularly limited, but it is not particularly limited, but it is possible to suppress filament refraction during molding and to mold the molded resin. From the viewpoint of body strength, 100 MPa or more is preferable, 200 MPa or more is more preferable, 300 MPa or more is further preferable, 350 MPa or more is particularly preferable, and 400 MPa or more is most preferable.

Further, E'(A) is preferably 3000 MPa or less, more preferably 2000 MPa or less, further preferably 1500 MPa or less, particularly preferably 1250 MPa or less, and most preferably 1000 MPa or less from the viewpoint of filament handleability.

Further, E'(A) can be adjusted by the composition of the resin, the three-dimensional regularity, and the like.

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

Further, the filament for three-dimensional modeling of the present invention may contain a filler, other resin and other additives described later in addition to the olefin resin composition (α). In this case, the content of the olefin 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 from the viewpoint of excellent heat resistance and formability, which is 60. By mass% or more is more preferable, 80% by mass or more is further preferable, 90% by mass or more is particularly preferable, and 95% by mass or more is most preferable.

Further, the content of the olefin resin composition (α) in the filament for three-dimensional modeling of the present invention is preferably 100% by mass or less, preferably 99% by mass or less, from the viewpoint of the strength of the modeled object and the addition of other functionality. Is more preferable, 98.5% by mass or less is further preferable, and 98% by mass or less is particularly preferable.

When the olefin-based resin composition (α) contains the olefin-based resin composition (A) and the resin composition (B) described later, the olefin-based resin composition (α) in the olefin-based resin composition (α) From the viewpoint of heat resistance, the content of A) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 70% by mass or more. preferable.

The content of the olefin resin composition (A) in the olefin resin composition (α) is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass from the viewpoint of formability. The following is more preferable, 80% by mass or less is particularly preferable, and 75% by mass or less is most preferable.

<Resin composition (B)>
The olefin-based resin composition (α) can contain the resin composition (B).
The resin composition (B) is not particularly limited as long as the amount of heat of crystallization (ΔHc (B)) measured at a temperature lowering rate of 10 ° C./min with a differential scanning calorimeter is less than 10 J / g. Absent. ΔHc (B) is preferably 9 J / g or less, more preferably 8 J / g or less, still more preferably 7 J / g or less, from the viewpoint that the amount of heat of crystallization of the olefin resin composition (α) can be easily adjusted. 6 J / g or less is particularly preferable.

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

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

Among them, the cyclic olefin resin is preferable from the viewpoint of kneadability with the olefin resin composition (A). The cyclic olefin resin is an olefin resin having an alicyclic structure in the molecular chain. Examples of the alicyclic structure include a monocyclic structure such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane, and a bicyclic structure such as norbornane, decalin, and spiropentane. These may be contained in the polymer main chain or the side chain, but in order to further enhance the kneadability and heat-sealing property with the olefin resin composition (A), they may be contained in the side chain. It is preferable that it is contained.

Cyclic olefin resins include copolymers of ethylene and cyclic olefins (cycloalkenes), copolymers of α-olefins and cyclic olefins (cycloalkenes), cyclic olefins (cycloalkenes), and cyclic olefins. Examples thereof include a hydrogenated compound of a ring-opening polymer, a hydride block copolymer which is a hydride of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit.

Among them, at least one aromatic vinyl monomer unit and at least one kind as a resin having an alicyclic structure in the side chain from the viewpoint of kneadability and heat-sealing property with the olefin resin composition (A). A hydride block copolymer, which is a hydride of the block copolymer containing the conjugated diene monomer unit of the above, is preferable. Further, the resin composition (B) may consist of one resin selected from the above, or may be a combination of a plurality of resins selected from the above.

The hydrogenated block copolymer is a hydrogenated product of a hydrogenated aromatic vinyl polymer block unit, which is a hydride of a polymer block composed of the aromatic vinyl monomer unit, and hydrogen, which is a hydride of a polymer block composed of the conjugated diene monomer unit. It has a modified conjugated diene polymer block unit. Further, the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit.

In addition, in this specification, a "block" means a polymerized segment of a copolymer which represents a microlayer separation from a polymerized segment which is structurally or compositionally different from the copolymer, as described later. For this reason, for example, "having at least two block units" means that the hydrogenated block copolymer has at least two polymerized segments of the copolymer representing microlayer separation from structurally or structurally different polymerized segments. Say that.

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

In the formula (1), R is a hydrogen atom or an alkyl group, Ar is a phenyl group, a halophenyl group, an alkylphenyl group, an alkylhalophenyl group, a naphthyl group, a pyridinyl group, or an anthrasenyl group.

The alkyl group may be a mono- or multiple-substituted alkyl group with a functional group such as a halo group, a nitro group, an amino group, a hydroxy group, a cyano group, a carbonyl group, and a carboxyl group. The alkyl group preferably has 1 to 6 carbon atoms. Further, the Ar is preferably a phenyl group or an alkylphenyl group, and more preferably a phenyl group.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene (including all isomers, particularly p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, and vinyl. Anthracene (all isomers), and mixtures thereof.

The conjugated diene monomer used as a raw material for the conjugated diene monomer unit may be a monomer having two conjugated double bonds, and is not particularly limited.

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

Polybutadiene, which is a polymer of 1,3-butadiene, has either a 1,2 configuration that gives an equivalent of 1-butane repeating units by hydrogenation, or a 1,4 configuration that gives an equivalent of ethylene repeating units by hydrogenation. Can be included.

The hydrogenated block copolymer composed of the aromatic vinyl monomer and the conjugated diene monomer containing 1,3-butadiene is included in the hydrogenated block copolymer used in the present invention. Preferably, the hydrogenated block copolymer is a functional group-free block copolymer. In addition, "without functional groups" means that there are no functional groups in the block copolymer, that is, there are no groups containing elements other than carbon and hydrogen.

Preferable examples of the hydrogenated aromatic vinyl polymer block unit include polystyrene hydride, and preferred examples of the hydrogenated conjugated diene polymer block unit include hydrogenated polybutadiene. A preferred embodiment of the hydrogenated block copolymer is a hydrogenated triblock or pentablock copolymer of styrene and butadiene, preferably free of any other functional group or structural modifier.

A "block" is defined as a polymerized segment of a copolymer that represents microlayer separation from structurally or compositionally different polymerized segments of the copolymer. Microlayer separation occurs due to the immiscibility of the polymerized segments in the block copolymer.

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

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.

If the ratio of hydrogenated aromatic vinyl polymer block units is equal to or higher than the above lower limit value, the rigidity does not decrease, and if it is equal to or lower than the above upper limit value, brittleness does not deteriorate.

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 at least the above lower limit value, brittleness does not deteriorate, and if it is at least the above upper limit value, rigidity does not decrease, so that the strength of the molded resin molded product is excellent. ..

The hydrogenated block copolymers are triblocks, multiblocks, tapered blocks, such as SBS, SBSBS, SIS, SISIS, and SISBS (where S stands for polystyrene, B stands for polybutadiene, and I stands for polyisoprene). Manufactured by hydrogenation of block copolymers, including star block copolymers.

The hydrogenated block copolymer contains a segment made of an aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer will have at least two hydrogenated aromatic vinyl polymer block units. Then, at least one hydrogenated conjugated diene polymer block unit will be provided between the two hydrogenated aromatic vinyl polymer block units.

The pre-hydrogenation block copolymer constituting the hydrogenation block may contain several additional blocks, and these blocks may be bonded to any position in the triblock polymer backbone. Thus, the linear block includes, for example, SBS, SBSB, SBBSS, and SBBSSB. The copolymer may be branched and the polymerization chain may be 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, still more preferably 45,000 or more, and particularly preferably 50,000 or more. The upper limit of Mw of the hydrogenated block copolymer is preferably 120,000 or less, more preferably 100,000 or less, still more preferably 95,000 or less, particularly preferably 90,000 or less, and most preferably 85,000 or less. , Very preferably 80,000 or less.

If the Mw of the hydrogenated block copolymer is at least the above lower limit value, the mechanical strength does not decrease, and if it is at least the above upper limit value, the molding processability does not deteriorate.
Mw herein is determined using gel permeation chromatography (GPC).

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

The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the rate at which the aromatic vinyl polymer block unit is saturated by hydrogenation, and the hydrogenation level of the conjugated diene polymer block unit is the conjugated diene polymer block. Indicates the rate at which the unit is saturated by hydrogenation. Such high levels of hydrogenation are preferred for heat resistance and transparency.

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

The glass transition temperature (Tg) of the resin composition (B) is not particularly limited, but is preferably 50 ° C. or higher, preferably 70 ° C. or higher, from the viewpoint of strength and heat resistance of the filament and the resin molded product formed by using the filament. Is more preferable, 80 ° C. or higher is further preferable, 90 ° C. or higher is particularly preferable, and 100 ° C. or higher is most preferable. The glass transition temperature (Tg) of the resin composition (B) is preferably 200 ° C. or lower from the viewpoint of kneadability with the olefin resin composition (A) and formability (suppression of warpage during modeling). 180 ° C. or lower is more preferable, 160 ° C. or lower is further preferable, 150 ° C. or lower is particularly preferable, and 140 ° C. or lower is most preferable.

Here, the glass transition temperature (Tg) is defined by raising the temperature of about 10 mg of a sample from room temperature to 250 ° C. at a heating rate of 10 ° C./min according to JIS K7121 using a differential scanning calorimeter (DSC). It is a value measured when the temperature is maintained for 1 minute, the temperature is lowered to 30 ° C. at a temperature lowering rate of 10 ° C./min, and the temperature is raised to 250 ° C. again at a temperature rising rate of 10 ° C./min.

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, still more preferably less than 50% by mass, from the viewpoint of heat resistance. , Less than 40% by mass is more preferable. Further, from the viewpoint of formability, the content is preferably more than 5% by mass, more preferably more than 10% by mass, further preferably more than 15% by mass, and particularly preferably more than 20% by mass. , 25% by mass or more is most preferable.

<Filament for 3D modeling>
The olefin resin composition (α) may be used in a shape suitable for the embodiment. Examples of the shape include pellets, powders, granules, filaments and the like. Above all, it is preferable to use it in a filament shape.

In addition to the olefin resin composition (α), the filament for three-dimensional modeling of the present invention includes fillers (organic particles, inorganic particles, reinforcing materials, etc.), other resins, and the like to the extent that the effects of the present invention are not impaired. May contain the components of.

Details of fillers (organic particles, inorganic particles, reinforcing materials, etc.) will be described below. Examples of other resins include PLA, polyester resin, polyamide resin, polyacetal resin and the like. Other components include heat resistant agents, UV absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slip agents, crystal nucleating agents, tackifiers, sealability improvers, antifogging agents, and mold release agents. Examples include agents, plasticizers, pigments, dyes, fragrances, flame retardants and the like.

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

Here, specific examples of the inorganic particles among the fillers include silica, alumina, kaolin, titanium dioxide, calcium carbonate, magnesium carbonate, zinc carbonate, calcium stearate, magnesium stearate, zinc stearate and the like.

Here, examples of the reinforcing material among the fillers include an inorganic filler and an inorganic fiber.
Specific examples of the inorganic filler include calcium carbonate, zinc oxide, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminate, magnesium silicate, potassium titanate, glass balloon, glass flakes, and glass powder. Silicon carbide, silicon nitride, boron nitride, gypsum, calcined kaolin, zinc oxide, antimony trioxide, zeolite, hydrotalcite, wallastonite, silica, talc, metal powder, alumina, graphite, carbon black, carbon nanotubes, etc. Be done.

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

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, preferably 5% by mass or more, based on 100% by mass of the resin composition (α). More preferably, 10% by mass or more is further preferable. Further, from the viewpoint of suppressing deterioration of the interlayer adhesiveness of the resin molded product to be molded, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less is further preferable.

<Manufacturing method of filament for 3D modeling>
The filament for three-dimensional modeling of the present invention is produced by 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. it can.

In the present invention, it is preferable to use a twin-screw extruder in the same direction from the viewpoint of dispersibility and miscibility of each component. Excellent dispersibility and miscibility are preferable because the accuracy and roundness of the filament diameter can be improved.

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

<Physical characteristics of filaments for 3D modeling>
The diameter of the three-dimensional molding filament of the present invention depends on the specifications of the system used for molding the 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. It is 1.6 mm or more, particularly preferably 1.7 mm or more. On the other hand, the diameter of the three-dimensional modeling filament 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.

Further, it is preferable that the accuracy of the diameter is within ± 5% with respect to an arbitrary measurement point of the filament from the viewpoint of stability of raw material supply. In particular, the three-dimensional modeling filament of the present invention has a standard deviation of diameter of preferably 0.07 mm or less, and particularly preferably 0.06 mm or less.

Further, the filament for three-dimensional modeling of the present invention has a roundness of preferably 0.93 or more, and particularly preferably 0.95 or more. The upper limit of roundness is 1.0. In this way, with a three-dimensional molding filament having a small standard deviation in diameter and high roundness, uneven ejection during molding is suppressed, and a resin molded body having excellent appearance and surface properties can be stably manufactured. can do. By using the above-mentioned olefin resin composition (α), a three-dimensional modeling filament satisfying such standard deviation and roundness can be produced relatively easily.

<Filament winding body for 3D modeling>
In manufacturing a resin molded body by a 3D printer using the 3D modeling filament of the present invention, the 3D modeling filament is stably stored and the 3D modeling filament is stably supplied to the 3D printer. Is required. Therefore, the filament for three-dimensional modeling of the present invention is packaged as a winding body wound around a bobbin, or the winding body is housed in a cartridge for long-term storage, stable feeding, and ultraviolet rays. It is preferable from the viewpoint of protection from environmental factors such as, twist prevention, and the like. Examples of the cartridge include a wound body wound around a bobbin, a structure in which a moisture-proof material or a moisture-absorbing material is used inside, and at least an orifice portion for feeding the filament is sealed.

Usually, a winding body in which a filament for 3D modeling is wound on a bobbin, or a cartridge containing the winding body is installed in or around the 3D printer, and the filament is always introduced from the cartridge into the 3D printer during molding. to continue.

<Manufacturing method of resin molded product>
In the method for producing a resin molded product of the present invention, a resin molded product is obtained by molding with a three-dimensional printer using the filament for three-dimensional molding of the present invention. Examples of the molding method using a 3D printer include a hot melting lamination method (ME method), a powder sintering method, an inkjet method, and a stereolithography method (SLA method). The filament for a 3D printer of the present invention is thermally melted. It is particularly preferable to use it in the lamination method. Hereinafter, the case of the Fused Deposition Modeling method will be described as an example.

A three-dimensional printer generally has a chamber, and in the chamber, a heatable base, an extrusion head installed in a gantry structure, a heating melter, a filament guide, a raw material supply unit such as a filament cartridge installation unit, etc. I have. In some 3D printers, the extrusion head and the heating / melting device are integrated.

By installing the extrusion head in the gantry structure, it can be arbitrarily moved on the XY plane of the base. The base is a platform for constructing a target three-dimensional object, support material, etc., and by heating and keeping warm, adhesiveness to the laminate can be obtained, and the obtained resin molded body can be used as a desired three-dimensional object to improve dimensional stability. It is preferable that the specifications are such that they can be used. Further, in order to improve the adhesiveness with the laminate, an adhesive glue may be applied on the substrate, or a sheet or the like having good adhesiveness with the laminate may be attached. Examples of the sheet having good adhesiveness to the laminate include a sheet having fine irregularities on the surface such as an inorganic fiber sheet, and a sheet made of the same type of resin as the laminate. Normally, at least one of the extrusion head and the substrate is 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 selectively printed. In this case, one of the polymers can be a modeling material for modeling a 3D object, and the other can be, for example, a supporting material needed as temporary equipment. The supporting material can then be removed, for example, by complete or partial dissolution in an aqueous system (eg, basic or acidic medium).

The three-dimensional modeling filament is unwound from the raw material supply unit, fed to the extrusion head by a pair of opposing rollers or gears, heated and melted by the extrusion head, and extruded from the tip nozzle. According to the signal transmitted based on the CAD model, the extrusion head moves its position and supplies the raw material onto the substrate for stacking and deposition. After this step is completed, the laminated deposit can be taken out from the substrate, and if necessary, the support material or the like can be peeled off or the excess portion can be cut off to obtain a resin molded body as a desired three-dimensional object. ..

The means for continuously supplying the raw material to the extrusion head is a method of feeding out filaments or fibers, a method of supplying powder or liquid from a tank or the like via a quantitative feeder, and plasticizing pellets or granules with an extruder or the like. An example is an example of a method of extruding and supplying the converted product. Among these, from the viewpoint of simplicity of the process and supply stability, the method of feeding and supplying the filament, that is, the method of feeding and supplying the above-mentioned three-dimensional modeling filament of the present invention is the most preferable.

When supplying filaments to a 3D printer, it is common to engage the filaments with drive rolls such as nip rolls and gear rolls and supply them to the extrusion head while taking them back. Here, in order to stabilize the raw material supply by strengthening the grip by the engagement between the filament and the drive roll, the minute uneven shape is transferred to the surface of the filament, and the frictional resistance with the engaging portion is increased. It is also preferable to add an inorganic additive, a spreading agent, an adhesive, a rubber, or the like to increase the size. If the filament has uneven thickness, gripping may not be possible due to engagement between the filament and the drive roll, and the drive roll may idle and the filament may not be supplied to the extrusion head.

In the three-dimensional modeling filament of the present invention, the temperature for obtaining appropriate fluidity for extrusion is usually about 180 to 300 ° C., which is a temperature that can be set by a normal three-dimensional printer. In the production method of the present invention, the temperature of the heat extrusion head is usually 290 ° C. or lower, preferably 200 to 280 ° C., and the substrate temperature is usually 120 ° C. or lower to stably produce the resin molded product.

The temperature (discharge temperature) of the molten resin discharged from the extrusion head is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, and preferably 300 ° C. or lower, preferably 290 ° C. or lower. More preferably, it is more preferably 280 ° C. or lower. When the temperature of the molten resin is at least the above lower limit value, it is preferable for extruding the resin having high heat resistance, and it is possible to discharge the molten resin at a high speed, which tends to improve the molding efficiency, which is preferable. On the other hand, when the temperature of the molten resin is not more than the above upper limit value, it is easy to prevent the occurrence of problems such as thermal decomposition of the resin, burning, smoke generation, odor, and stickiness. Further, when the temperature of the molten resin is equal to or lower than the above upper limit value, generally, fragments of the molten resin called stringing and lumps of excess resin called lumps adhere to the resin molded body. It is also preferable from the viewpoint of preventing deterioration of the appearance.

The molten resin discharged from the extrusion head is preferably discharged in the form of a strand having a diameter of 0.01 to 1.0 mm, more preferably 0.02 to 0.5 mm in diameter. It is preferable that the molten resin is discharged in such a shape because the reproducibility of the CAD model tends to be good.

High-speed modeling in the three-dimensional modeling filament 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, further preferably 7 mm / s or more, and most preferably 10 mm / s or more. The upper limit is not particularly limited, but the faster the speed, the more preferable. However, the molding speed is preferably 100 mm / s or less, more preferably 80 mm / s or less, and more preferably 60 mm / s, in order to have a speed at which there is no problem in formability such as bending of the filament described above and deterioration of appearance described later. The following is more preferable.

When manufacturing a resin molded product by a 3D printer using a filament for 3D modeling, when making a molded product while laminating the strand-shaped resin discharged from the extrusion head, the strands of the resin discharged earlier are used. On the surface of the molded product, uneven portions (streaks, etc.) may occur due to insufficient adhesion to the resin strands discharged on the resin strands or uneven discharge. If such uneven portions are present on the surface of the molded product, not only the appearance may be deteriorated, but also problems such as the molded product being easily damaged may occur.

The filament for three-dimensional molding of the present invention has good adhesiveness between the resin strands discharged earlier and the resin strands discharged on the strands, and has a high elastic modulus near room temperature, so that the filaments can be bent. Since it is difficult to occur, that is, the roundness of the diameter is high, uneven ejection during molding is suppressed, and a molded product having excellent appearance, surface texture, etc. can be stably manufactured.

When making a molded product while laminating the strand-shaped resin discharged from the extrusion head by a three-dimensional printer, there is a step of stopping the resin discharge and then moving the nozzle to the laminating point in the next step. At this time, the resin is not interrupted and fine resin fibers are generated, which may remain on the surface of the molded product as if a thread was pulled. When the above-mentioned stringing occurs, problems such as deterioration of the appearance of the molded product may occur.

The filament for three-dimensional molding of the present invention has a high elastic modulus near room temperature and is unlikely to bend, that is, the standard deviation of the diameter is small, the roundness is high, and the crystallization rate is moderate and the fracture is high. Since it has strain, stringing is suppressed, and a molded product having excellent appearance, surface texture, etc. can be stably produced.

The resin molded product of the present invention may promote or complete crystallization by heat treatment after molding, depending on the intended use.

In producing the resin molded product of the present invention, the supporting material may be molded at the same time. The type of supporting material is not particularly limited, and examples thereof include BVOH (butenediol vinyl alcohol), PVOH (polyvinyl alcohol), EVOH (ethylene-vinyl alcohol copolymer), and HIPS (haimpact polystyrene).

(Use of resin molded product)
The resin molded product of the present invention is excellent in strength and heat resistance. The use is not particularly limited, but stationery; toys; covers for mobile phones and smartphones; parts such as grips; school teaching materials, home appliances, repair parts for OA equipment, various parts such as automobiles, motorcycles, and bicycles. It can be suitably used for applications such as electric / electronic equipment materials, agricultural materials, horticultural materials, fishery materials, civil engineering / building materials, and medical supplies.

Although the following will be described in more detail in Examples, the present invention is not limited by these. The various measured values and evaluations displayed in the present specification were performed as follows.

(1) Crystallization heat (ΔHc) and crystallization temperature (Tc)
Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., trade name "Pyris1 DSC", the temperature of about 10 mg of the sample was raised from 0 ° C. to 250 ° C. at a heating rate of 10 ° C./min according to JIS K7122. The calorific value of crystallization (ΔHc) and the crystallization temperature (Tc) (both are temperature lowering processes) were determined from the thermogram measured when the temperature was kept at the temperature for 1 minute and then the temperature was lowered to 0 ° C. at a temperature lowering rate of 10 ° C./min. ..

(2) Crystal melting temperature (Tm), glass transition temperature (Tg)
Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., trade name "Pyris1 DSC", about 10 mg of the sample was heated from 0 ° C to 250 ° C at a heating rate of 10 ° C / min according to JIS K7121. After holding at the temperature for 1 minute, the temperature was lowered to 0 ° C. at a temperature lowering rate of 10 ° C./min, and again, the crystal melting temperature (crystal melting temperature) was measured from each thermogram measured when the temperature was raised to 250 ° C. at a heating rate of 10 ° C./min. Tm) (° C.) (reheating process) was determined.

(3) Storage elastic modulus at 40 ° C. (E')
The filaments obtained in Examples and Comparative Examples were formed into sheets having a thickness of about 0.5 mm by heat pressing to prepare samples for measurement. Using a dynamic viscoelasticity measuring machine (manufactured by IT Measurement Co., Ltd., trade name: viscoelasticity spectrometer DVA-200), vibration frequency: 10 Hz, heating rate: 3 ° C./min, strain 0.1%. The storage elastic modulus (E') was measured from −100 ° C. to 250 ° C., and the storage elastic modulus (E ′) at 40 ° C. was obtained from the obtained data.

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

〇: When modeling was performed at a modeling speed of 10 mm / s, the modeling could be completed without bending of the filament during modeling.
X: When molding was performed at a molding speed of 10 mm / s, the filament was bent in the middle (or from the beginning), and the molding 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 the dumbbell-shaped sample (sample 1) produced by the warp evaluation during molding, which will be described later, were measured. The maximum tensile strength (Z-axis strength) and breaking elongation of the following sample 2 in the Z-axis direction were measured. Moreover, the value of Z-axis strength / horizontal strength was calculated. The larger the horizontal strength and the Z-axis strength, the more preferable it is. Further, the larger the value of the elongation at break, the more preferable it is. In particular, the closer the Z-axis strength / horizontal strength is to 1, the better.

Sample 2 was produced as follows.
That is, a dumbbell-shaped sample (length 75 mm, width 10 mm, thickness 5 mm) is used as a 3D printer (manufactured by Muto Kogyo Co., Ltd., trade name: MF-2200D) with the sample length direction as the Z-axis direction (stacking direction). Was modeled using. At that time, PP tape (3M Scotch 315SN) was attached to the modeling table, and sample 2 was produced 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 adhesiveness>
Tensile tests were performed on Samples 1 and 2 under the conditions of an initial chuck distance of 45 mm, a speed of 50 mm / min, and 23 ° C., and the interlayer adhesiveness was evaluated from the measured maximum tensile strength based on the following criteria.

〇: Maximum tensile strength of sample 2 (Z-axis strength) / Maximum tensile strength of sample 1 (horizontal strength) ≥ 0.4
Δ: 0.4> Maximum tensile strength of sample 2 (Z-axis strength) / Maximum tensile strength of sample 1 (horizontal strength) ≧ 0.25
X: 0.25> Maximum tensile strength of sample 2 (Z-axis strength) / Maximum tensile strength of sample 1 (horizontal strength)

<Warp during modeling>
The evaluation sample (this was designated as sample 1) was produced as follows.
That is, a dumbbell-shaped sample (length 75 mm, width 10 mm, thickness 5 mm) is used as a 3D printer (manufactured by Mutoh Industries, Ltd., trade name: MF-2200D) with the sample thickness direction as the Z-axis direction (stacking direction). Was modeled using. At that time, PP tape (3M Scotch 315SN) is attached to the modeling table, and an evaluation sample is 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%. did.

After manufacturing the evaluation sample, the evaluation sample was removed from the modeling table and placed on a horizontal surface. At that time, the distances between the four corners of the evaluation sample and the horizontal plane were measured, and the average value of the obtained values was taken as the amount of warpage. From this amount of warpage, the warp at the time of modeling was evaluated based on the following criteria. Among the following criteria, the smaller the value of the warp amount, the more preferable it is.

〇: The amount of warpage was less than 3 mm.
X: The amount of warpage was 3 mm or more, or a large warp occurred during modeling, so that modeling could not be completed.

The raw materials used in the examples and comparative examples are as follows.

<Olefin resin composition (A)>
(A-1); manufactured by Japan Polypropylene Corporation, trade name: Wellnex RMG02, reactor TPO, Tm: 130 ° C., Tc: 86 ° C., ΔHc: 44J / g, E': 340MPa, composition ratio (mass ratio): Propylene / ethylene = 95/5
(A-2); manufactured by Japan Polypropylene Corporation, trade name: Wintech WMG03, propylene and ethylene random polymer, Tm: 142 ° C, Tc: 106 ° C, ΔHc: 80J / g, E': 1200MPa, composition ratio (Mass ratio): Propylene / ethylene = 98/2

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

(Example 1)
80 parts by mass of olefin resin (A-1) and 20 parts by mass of resin (B-1) are mixed, and the melting temperature is 200 ° C. from a nozzle with a diameter of 2.5 mm using a 20 mmφ isodirectional biaxial kneader. After extrusion, the mixture was cooled in cooling water at 30 ° C. to obtain a filament having a diameter of 1.75 mm. Table 1 shows the results of various evaluations of this filament.

(Example 2)
In Example 1, 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. did. Table 1 shows the results of various evaluations of this filament.

(Example 3)
Filaments were produced in the same manner as in Example 2 except that the olefin resin composition (A-1) was changed to the olefin resin composition (A-2) in Example 2. Table 1 shows the results of various evaluations of this filament.

(Example 4)
In Example 2, filaments were produced in the same manner as in Example 2 except that the resin (B-1) was changed to the resin (B-2). Table 1 shows the results of various evaluations of this filament.

(Comparative Example 1)
In Example 1, filaments were 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). Table 1 shows the results of various evaluations of this filament.

(Comparative Example 2)
In Example 1, filaments were 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). Table 1 shows the results of various evaluations of this filament.

In the evaluation of warpage during modeling using the filament of Comparative Example 2, the modeling could not be completed because a large warp occurred during modeling. Therefore, the warp evaluation at the time of modeling was performed using a modeled object in the middle of modeling. Further, in the evaluation of the horizontal strength, since a modeled product capable of a tensile test could not be obtained, a 0.5 mm thick sheet obtained by heat-pressing the filament was cut into 5 mm wide strips instead.

(Comparative Example 3)
Table 1 shows the results of various evaluation results using a commercially available PP filament (manufactured by Mutoh Industries, Ltd., product name: Value3D MagiX material, PP, 1.75 mm).

Regarding the filament of Comparative Example 3, a thermogravimetric measuring device (manufactured by TA Instruments Japan, TGA Q5000IR) was used to raise the temperature from room temperature to 700 ° C. in air at a heating rate of 20 ° C./min. The temperature was raised, the amount of the obtained residue was measured, and the IR measurement of the residue was carried out. From the results, it was determined that the filament of Comparative Example 3 contained 39% by mass of talc.

Further, "24 × ΔHc—E'" in Examples 1 to 4 and Comparative Examples 1 and 2 is a value relating to a filament composed of at least one of the olefin resin composition (A) and the resin composition (B). , “24 × ΔHc—E ′” in Comparative Example 3 is a value relating to a filament containing talc. That is, “24 × ΔHc—E ′” in Comparative Example 3 is different from the above equation [1].

From Table 1, since the filaments of Examples 1 to 4 satisfy the above formula [1], they are filaments having excellent formability such as suppression of warpage during modeling while maintaining high-speed formability.

Further, the filaments of Examples 1 and 2 have the same or higher interlayer adhesiveness as those of the filament made of the low crystallinity olefin resin composition (A) (Comparative Example 1), and the resin composition. It can be seen that the substance (B-1) does not inhibit the interlayer adhesiveness.

Further, by comparing Example 2 and Example 4, in Example 2 using the resin composition (B-1) having a cyclic structure in the side chain, the resin composition (B-2) having a cyclic structure in the main chain. It can be seen that higher Z-axis strength and interlayer adhesiveness are obtained than in Example 4 using).

On the other hand, the filament of Comparative Example 1 has a low storage elastic modulus measured at 40 ° C. and 10 Hz, so that the filament is easily bent and is inferior in high-speed formability.
On the other hand, since the filament of Comparative Example 2 has a large ΔHc, it has a large warp during modeling and is inferior in formability.
Further, the filament of Comparative Example 3 has a high-speed formability and a warp suppressing effect, but has a low interlayer adhesiveness. It is considered that this is because talc hinders 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 invention. This application is based on a Japanese patent application filed on October 2, 2019 (Japanese Patent Application No. 2019-182009), the contents of which are incorporated herein by reference.

Claims (11)

1. A three-dimensional modeling filament containing an olefin resin composition (α) satisfying the following formula [1].
   700 ≧ 24 × ΔHc (α) -E'(α) ... [1]
   ΔHc (α): The amount of heat of crystallization (J / g) when the olefin resin composition (α) was measured with a differential scanning calorimeter at a temperature lowering rate of 10 ° C./min.
   E'(α): Storage elastic modulus (MPa) of the olefin resin composition (α) measured at 40 ° C. and 10 Hz.
2. The three-dimensional modeling filament according to claim 1, wherein the ΔHc (α) is 75 J / g or less.
3. The three-dimensional modeling filament according to claim 1 or 2, wherein the E'(α) is 350 MPa or more.
4. The olefin-based resin composition (α) contains the olefin-based resin composition (A) and the resin composition (B).
   The resin composition (B) has a crystallization heat quantity (ΔHc (B)) of less than 10 J / g when measured with a differential scanning calorimeter at a temperature lowering rate of 10 ° C./min, according to claims 1 to 3. The filament for three-dimensional modeling according to any one of the items.
5. The crystallization temperature when measured at a temperature decrease rate of 10 ° C./min by the differential scanning calorimeter of the olefin resin composition (A) and 10 by the differential scanning calorimeter of the olefin resin composition (α). The three-dimensional molding filament according to claim 4, wherein the difference from the crystallization temperature when measured at a temperature lowering rate of ° C./min is 10 ° C. or less.
6. The olefin-based resin composition (α) contains the olefin-based resin composition (A), and the olefin-based resin composition (α) contains the olefin-based resin composition (A).
   The olefin resin composition (A) is a propylene homopolymer, a random copolymer of ethylene and at least one monomer of α-olefin having 4 to 12 carbon atoms and propylene, ethylene and α having 4 to 12 carbon atoms. -A block copolymer of at least one monomer of olefin and propylene, a blend of at least one maleic anhydride graft polypropylene, propylene and polyethylene and ethylene-propylene rubber, and at least one of propylene and polyethylene and ethylene-propylene rubber. A dynamically crosslinked product, a polymer of at least one of propylene and polyethylene and an ethylene-propylene rubber, at least one resin composition selected from the group consisting of high density polyethylene, low density polyethylene, and linear low density polyethylene. The filament for three-dimensional modeling according to any one of claims 1 to 5.
7. The olefin-based resin composition (α) contains the resin composition (B),
   The three-dimensional modeling filament according to any one of claims 1 to 6, wherein the resin composition (B) contains a cyclic olefin resin.
8. The three-dimensional modeling filament according to any one of claims 1 to 7, further containing a filler.
9. A resin molded product containing the three-dimensional molding filament according to any one of claims 1 to 8.
10. The wound body of the filament for three-dimensional modeling according to any one of claims 1 to 8.
11. A three-dimensional modeling cartridge containing the three-dimensional modeling filament according to any one of claims 1 to 8.