JP2019130864A - Three-dimensional molding material, three-dimensional molding filament, wound body of the filament, and three-dimensional molding cartridge - Google Patents

Abstract

To provide a 3D molding material and a filament for 3D molding suitably used for industrial application that have heat resistance and strength of a shaped article, and good workability, in which warpage during shaping is suppressed without precise temperature control of a molding area.SOLUTION: A three-dimensional material used for a three-dimensional printer of a hot-melt lamination system has a shear storage modulus (G') measured at 100°C and 1 Hz of 1.00×10Pa or less.SELECTED DRAWING: None

Description

  The present invention relates to a material for three-dimensional modeling and a filament for three-dimensional modeling that have good moldability by a hot melt lamination type three-dimensional printer. The present invention also relates to a wound body of this filament and a cartridge for three-dimensional modeling.

  Today, three-dimensional printers of various additive manufacturing methods (for example, a binder injection method, a hot melt lamination method, a liquid tank photopolymerization method, etc.) are on the market.

  Among them, in the hot melt laminating method (hereinafter sometimes referred to as FDM (Fused Deposition Modeling) method), the raw material is first inserted into the extrusion head as a filament made of a thermoplastic resin, and is heated and melted in the extrusion head. It is continuously extruded from the provided nozzle part onto the XY plane substrate in the chamber. The extruded resin is deposited and fused on the resin laminate that has already been deposited, and solidifies together as it cools. Since the FDM method is such a simple system, it has been widely used.

  In a material extrusion type three-dimensional printer typified by the FDM method, normally, the extrusion process is repeated while the nozzle position rises in the Z-axis direction perpendicular to the XY plane. A dimensional object is constructed.

  Conventionally, as a raw material used for a material for molding by hot melt lamination, generally, polylactic acid (hereinafter sometimes referred to as “PLA resin”) or acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”). Have been used suitably from the viewpoint of processability and fluidity (Patent Document 1). In recent years, filaments such as polypropylene (PP) and elastomers have been put to practical use in addition to these. In particular, since ABS resin and PP are excellent in heat resistance and strength of shaped products, they are widely used including industrial uses such as shaping of products and production tools.

  On the other hand, since ABS resin and PP have large warpage during molding, there is a problem that it is difficult to peel off from a modeling table during modeling or to obtain a target modeled object with high dimensional accuracy. Therefore, for example, in Patent Document 2, this warpage is suppressed by precisely controlling the temperature of the modeling area.

JP 2008-194968 A Japanese translation of PCT publication No. 2002-500584

  However, the method of precisely controlling the temperature of the modeling area as described in Patent Document 2 has a problem that the 3D printer device is large and expensive. On the other hand, although the 3D printer that cannot control the temperature of the modeling area is inexpensive, the above-described problem of warpage occurs.

  In view of the above-mentioned problems of the prior art, the object of the present invention is also suitable for industrial applications where heat resistance is required and warping during modeling is suppressed without precise temperature control of the modeling area. It is to provide a three-dimensional modeling material and a three-dimensional modeling filament to be used. Furthermore, in addition to suppressing warping during modeling, it is desirable to have heat resistance during modeling, strength of a modeled article, and good workability.

As a result of intensive studies to solve the above problems, the present inventors have found that a three-dimensional modeling material having a specific shear storage modulus (G ′) can solve the above problems.
That is, the gist of the present invention resides in the following [1] to [13].
[1] A three-dimensional modeling material used for a hot-melt lamination type three-dimensional printer, and a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is 1.00 × 10 ⁷ Pa or less. 3D modeling material.
[2] A homogeneous three-dimensional material made of one kind of resin or a mixture of two or more kinds of resins, and having a shear storage elastic modulus (G ′) measured at 100 ° C. and 1 Hz, The material for three-dimensional modeling according to [1], which is 0.90 × 10 ⁷ Pa or less.
[3] The three-dimensional modeling material according to [1], which has a multilayer structure using two or more kinds of resins in different layers.
[4] In any one of [1] to [3], the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz contains a thermoplastic resin (A) of 1.00 × 10 ⁷ Pa or less. The three-dimensional modeling material described.
[5] The three-dimensional structure according to [4], further including a thermoplastic resin (B) having a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz of greater than 1.00 × 10 ⁷ Pa. Materials.
[6] Thermoplastic resin (A) having a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz of 1.00 × 10 ⁷ Pa or less, and shear storage modulus (G) measured at 100 ° C. and 1 Hz ′) Is a multilayer structure containing a thermoplastic resin (B) greater than 1.00 × 10 ⁷ Pa and containing the thermoplastic resin (A) and the thermoplastic resin (B) in different layers. The material for three-dimensional modeling as described in [3].
[7] The three-dimensional modeling material according to [6], wherein at least a part of the surface of the three-dimensional modeling material is a layer containing the thermoplastic resin (A).
[8] The three-dimensional modeling material according to any one of [1] to [7], wherein a tensile storage elastic modulus (E ′) measured at 100 ° C. and 10 Hz is 100 MPa or more.
[9] A three-dimensional modeling filament comprising the three-dimensional modeling material according to any one of [1] to [8], wherein the filament diameter is 1.0 to 5.0 mm. .
[10] The three-dimensional modeling filament according to [9], wherein the multilayer structure is a core-sheath structure.
[11] The three-dimensional modeling filament according to [9] or [10], wherein in the core-sheath structure, 10% or more of the filament diameter is a core part.
[12] A wound body of the three-dimensional modeling filament according to any one of [9] to [11].
[13] A cartridge for a three-dimensional printer in which the three-dimensional modeling filament according to any one of [9] to [11] is stored in a container.

  ADVANTAGE OF THE INVENTION According to this invention, the three-dimensional modeling material and the three-dimensional modeling filament which were excellent in the moldability by the three-dimensional printer of a melt lamination system are provided. Specifically, it is possible to provide a material that has high strength and heat resistance of a shaped product, and that has suppressed warping during modeling even without precise temperature control of the modeling area. Furthermore, preferably, a material having heat resistance that can suppress deformation due to heat during modeling can be provided. As a result, it is possible to provide a three-dimensional modeling material that is also suitably used for industrial applications.

It is a schematic diagram explaining the multilayer structure in the three-dimensional modeling material of this invention.

  Hereinafter, embodiments of the three-dimensional modeling material of the present invention will be described in detail. The present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

[3D modeling material]
The three-dimensional modeling material of the present invention is a three-dimensional modeling material used in a hot melt lamination type three-dimensional printer, and has a shear storage elastic modulus (G ′) measured at 100 ° C. and 1 Hz of 1.00. It is characterized by being 10 ⁷ Pa or less.

[Physical properties of 3D modeling materials]
The three-dimensional modeling material of the present invention has a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz of 1.00 × 10 ⁷ Pa or less. Preferably it is 0.90 × 10 ⁷ Pa or less, more preferably 0.80 × 10 ⁷ Pa or less, preferably 0.60 × 10 ⁷ Pa or less. By setting it to the upper limit value or less, it is possible to suppress warping during modeling during modeling in the three-dimensional modeling material. Specifically, by setting the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz below the upper limit value, the temperature at which the resin solidifies after ejection from the nozzle of the 3D printer during modeling, and the modeling atmosphere temperature It is considered that the warpage is suppressed because the difference between the difference and the amount of shrinkage due to linear expansion after solidification becomes small. In addition, from the viewpoint of heat resistance during modeling, 0.001 × 10 ⁷ Pa or more is preferable, more preferably 0.050 × 10 ⁷ Pa or more, and further preferably 0.090 × 10 ⁷ Pa or more, More preferably, it is 0.10 × 10 ⁷ Pa or more, and further preferably 0.15 × 10 ⁷ Pa or more. If the heat resistance at the time of modeling is insufficient, there is a concern that the model is deformed during modeling, resulting in a modeling failure.

  The composition for the three-dimensional modeling material having the above-described shear storage modulus (G ′) is not particularly limited as will be described later. For example, from a styrene resin, an olefin resin, polylactic acid (PLA), and a polyester resin. The number of monomers constituting these resins can be appropriately selected, or resins having different shear storage moduli (G ′) and storage moduli (E ′) or different can be selected. This G ′ can be achieved by using a resin having Tg together or adding rubber particles.

In particular, when the three-dimensional modeling material of the present invention is a homogeneous three-dimensional modeling material made of one type of resin or a mixture of two or more resins, shear storage measured at 100 ° C. and 1 Hz. The elastic modulus (G ′) is preferably 0.90 × 10 ⁷ Pa or less, more preferably 0.55 × 10 ⁷ Pa or less, from the viewpoint of suppressing warpage during modeling.

In the three-dimensional modeling material of the present invention, the tensile storage elastic modulus (E ′) at 100 ° C. is preferably 1000 MPa or less, more preferably 900 MPa or less, from the viewpoint of suppressing warpage during modeling. Moreover, it is preferable that it is 100 Mpa or more from a viewpoint of the heat resistance at the time of modeling and modeling. If the heat resistance of the shaped object is insufficient, the shaped object may be deformed at a high temperature. In addition, if the heat resistance at the time of modeling is insufficient, there is a concern that the modeled object may be deformed during modeling, resulting in poor modeling.
The three-dimensional modeling material of the present invention has a tensile storage modulus (E ′) at 30 ° C. of preferably 100 MPa or more, preferably 400 MPa or more from the viewpoint of the strength of the filament and the modeled article at room temperature. Preferably, 800 MPa or more is more preferable, and 1000 MPa or more is more preferable. Usually, it is about 5000 MPa or less.
In this specification, generally known methods can be used as a method for measuring each storage elastic modulus, and it is not particularly limited. Specifically, it is preferable to measure under the conditions described in the examples described later. .

When the three-dimensional modeling material of the present invention is made of a styrene-based resin described later, the melt index (MI) measured at 220 ° C. and 10 kg is preferably 10 or more and 100 or less. More preferably, it is 20 or more, More preferably, it is 30 or more, More preferably, it is 90 or less, More preferably, it is 80 or less. Moreover, when it consists of the polyolefin-type resin mentioned later, it is preferable that the melt index (MI) when measured at 190 degreeC and 10 kg is 10 or more and less than 150, and it is more preferable that it is 20 or more and less than 120. . If it is above the lower limit value, it is preferable because the high-speed modeling property during three-dimensional modeling tends to be good, and if it is not more than the upper limit value, the molecular weight is not too low and it tends to be excellent in strength.
In the present specification, measurement may be performed according to JISK7210 using a melt index measuring device. Although conditions, such as temperature at the time of measurement, are not specifically limited, Specifically, it is preferable to measure on the conditions as described in the below-mentioned Example.

[Thermoplastic resin (A)]
The composition for the three-dimensional modeling material of the present invention is not particularly limited as long as it has a specific G ′, but the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is 1.00 × 10 ⁷ Pa. It is preferable to contain the following thermoplastic resin (A). By containing the thermoplastic resin (A), it becomes easy to adjust the shear storage elastic modulus (G ′) measured at 100 ° C. and 1 Hz of the material for three-dimensional modeling to 1.00 × 10 ⁷ Pa or less, Since it exists in the tendency which can suppress the curvature at the time of modeling, it is preferable.

(Physical properties)
The thermoplastic resin (A) used for the three-dimensional modeling material of the present invention has a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz of 1.00 × 10 ⁷ Pa or less. Preferably it is 0.90 * 10 < ⁷ > or less, More preferably, it is 0.80 * 10 < ⁷ > or less, More preferably, it is 0.60 * 10 < ⁷ > or less. By setting it to the upper limit value or less, it is possible to suppress warping during modeling during modeling in the three-dimensional modeling material. Moreover, it is preferable that it is 0.001 * 10 < ⁷ > or more from a heat resistant viewpoint at the time of modeling. If the heat resistance at the time of modeling is insufficient, there is a concern that the model is deformed during modeling, resulting in a modeling failure.

  The composition of the thermoplastic resin having the above-mentioned shear storage modulus (G ′) is not particularly limited as described later. For example, styrene resin, olefin resin, polylactic acid (PLA), and amorphous polyester resin ( 1 or more selected from polyester-based resins such as PETG), and this G ′ can be achieved by appropriately selecting the types of monomers constituting these resins and adding rubber particles. it can. Especially, it is preferable to select a styrene resin or an olefin resin as a main component from the viewpoint of excellent low moisture absorption, impact resistance, and strength. In this case, a main component is a component which occupies 50 wt% or more among thermoplastic resins (A).

The thermoplastic resin (A) used for the three-dimensional modeling material of the present invention has a tensile storage elastic modulus (E ′) measured at 100 ° C. and 10 Hz, in terms of warpage suppression during modeling and interlayer adhesion strength of the modeled object. Therefore, 500 MPa or less is preferable, 350 MPa or less is more preferable, and 100 MPa or less is more preferable. It is preferable that it is 1 Mpa or more from a viewpoint of the heat resistance at the time of modeling and modeling.
The tensile storage modulus (E ′) measured at 100 ° C. and 10 Hz can be adjusted by the resin composition, copolymerization ratio, and the like.

Moreover, the thermoplastic resin (A) used for the three-dimensional modeling material of the present invention has a tensile storage elastic modulus (E ′) measured at 30 ° C. and 10 Hz, and the room temperature of the three-dimensional modeling material and the modeled article obtained. From the viewpoint of strength at 100, 100 Ma or more is preferable, 200 MPa or more is more preferable, and 500 MPa or more is more preferable. Usually, it is about 5000 MPa or less.
The tensile storage modulus (E ′) measured at 30 ° C. and 10 Hz can be adjusted by the resin composition, copolymerization ratio, and the like.

(Styrene resin)
The thermoplastic resin (A) used for the three-dimensional modeling material of the present invention can be a resin containing a styrene resin. Here, the styrene resin is a resin having a structural unit derived from at least an aromatic vinyl monomer, and preferably a resin having a structural unit derived from styrene. Furthermore, as necessary, it has structural units derived from vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, conjugated diene monomers, other vinyl monomers, and the like. May be.

  Styrenic resins are aromatic vinyl monomers and, if necessary, vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, conjugated diene monomers, and / or copolymers with these. A monomer mixture containing other possible vinyl monomers can be obtained by subjecting to a known block polymerization, block suspension polymerization, solution polymerization, precipitation polymerization or emulsion polymerization.

The aromatic vinyl monomer is not particularly limited, and specific examples include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, o-ethyl styrene, p-ethyl styrene, and pt-butyl. Examples include styrene. Of these, styrene or α-methylstyrene is preferably used. One or more of these can be used. The monomer component constituting the styrene resin preferably contains 20% by weight or more of an aromatic vinyl monomer, more preferably 50% by weight or more.
The vinyl cyanide monomer is not particularly limited, and specific examples include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like. Of these, acrylonitrile is preferably used. One or more of these can be used.

  Although there is no restriction | limiting in particular about an unsaturated carboxylic-acid alkylester type monomer, The ester of C1-C20 alcohol and (meth) acrylic acid is suitable. Such an ester may further have a substituent, and examples of the substituent include a hydroxyl group and chlorine. Specific examples of unsaturated carboxylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) T-butyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Examples thereof include 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate and 2,3,4,5-tetrahydroxypentyl (meth) acrylate. One or more of these can be used. Here, “(meth) acrylic acid” represents acrylic acid or methacrylic acid.

  The conjugated diene monomer is not particularly limited, but 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like are preferable, and 1,3-butadiene, isoprene or 1,3-pentadiene is preferable. More preferably, it is 1,3-butadiene or isoprene.

  Other vinyl monomers include aromatic vinyl monomers, and optionally vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, and conjugated diene monomers. There is no particular limitation as long as it can be polymerized, and specific examples thereof include maleimide monomers such as N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, maleic acid, Maleic acid monoethyl ester, maleic anhydride, phthalic acid, itaconic acid, and other vinyl monomers having a carboxyl group or a carboxyl group, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4 -Hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-pro , Cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, vinyl monomers having a hydroxyl group such as 4,4-dihydroxy-2-butene, acrylamide, methacrylamide, N- Methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N- Vinyl monomers having amino groups or derivatives thereof such as vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropyl Propenyl - oxazoline, 2-vinyl - oxazoline, 2-acryloyl - oxazoline and 2-styryl - vinyl-based monomer having oxazoline group such as oxazoline. One or more of these can be used.

  The molecular weight of the styrenic resin is not limited, but the viewpoint of securing the extrusion stability when producing filaments obtained using modeling materials and the mechanical strength necessary for winding the filaments around bobbins and collecting them Accordingly, the weight average molecular weight (Mw) is preferably 50,000 or more, and more preferably 80,000 or more. On the other hand, from the viewpoint of further reducing the melt viscosity at low temperature of the filament obtained using the modeling material, 400,000 or less is preferable. The weight average molecular weight here refers to a polystyrene-reduced weight average molecular weight measured by GPC using chloroform as a solvent.

  Specific examples of the styrene resin used for the three-dimensional modeling material of the present invention include, for example, acrylonitrile-butadiene-styrene (ABS) resin, methyl methacrylate-butadiene-styrene (MBS) resin, butadiene-styrene resin, and the like. Can be mentioned. Specific examples of the ABS resin include HF-3 and EX19C manufactured by UMG ABS Co., Ltd., and GT-R-61A manufactured by Denka Co., Ltd. Examples of the MBS resin include Estyrene MBS manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and Clearen TH-11 manufactured by Denka Co., Ltd. Examples of the butadiene-styrene resin include Clearen 730L manufactured by Denka Co., Ltd.

In the styrenic resin, the thermoplastic resin (A) is selected from monomers such that the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is 1.00 × 10 ⁷ Pa or less. It is preferable. For example, the styrene resin (A) used as the thermoplastic resin (A) preferably includes a structural unit derived from an unsaturated carboxylic acid alkyl ester monomer. Among them, a structural unit derived from a (meth) acrylic acid ester is more preferable, and from the viewpoint that the target G ′ can be achieved, an acrylic acid ester having an alcohol-derived hydrocarbon group having 1 to 20 carbon atoms, and The alcohol group-derived hydrocarbon group includes a structural unit derived from at least one selected from the group consisting of methacrylic acid esters having 2 to 20 carbon atoms. Particularly preferably, it includes a structural unit derived from an acrylate ester having 1 to 20 carbon atoms in the alcohol-derived hydrocarbon group from the viewpoint that the target G ′ can be achieved even if the copolymerization ratio is kept low. .

  Specific examples of (meth) acrylic acid esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Acrylic acid ester having 1 to 20 carbon atoms in the hydrocarbon group and methacrylic acid ester having 2 to 20 carbon atoms in the alcohol-derived hydrocarbon group are preferable, and the desired Tg is achieved even if the copolymerization rate is kept low. From the viewpoint that it can be produced, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like are more preferable.

From the viewpoint of setting the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz to 1.00 × 10 ⁷ Pa or less, the copolymerization ratio of the structural units is preferably 1 wt% or more with respect to the entire styrene resin. 2 wt% or more is more preferable. Further, from the viewpoint of maintaining the heat resistance and strength of the styrene resin and maintaining the post-processability, it is preferably less than 10 wt%, more preferably less than 8 wt%.

In addition, from the viewpoint of improving the color developability of the finally obtained three-dimensional modeling material, it is preferable to further contain methyl methacrylate as the unsaturated carboxylic acid alkyl ester monomer.
The copolymerization ratio of methyl methacrylate is preferably 5 wt% or more from the viewpoint of color development, and more preferably 10 wt% or more. Moreover, 60 wt% or less is preferable and 50 wt% or less is more preferable from a viewpoint of the intensity | strength and impact resistance of a three-dimensional modeling material and a modeling thing, and post-processability maintenance.
Moreover, it is preferable that a styrene resin (A) contains the structural unit derived from a conjugated diene monomer. Examples of the conjugated diene monomer include 2-methyl-1,3-butadiene, 2,4-hexadiene, 1,3-butadiene and the like. Among them, 1,3-butadiene is preferable from the viewpoint of impact resistance. Preferably there is.
From the viewpoint of impact resistance of the styrene resin (A), the copolymerization ratio of the conjugated diene monomer is preferably 1 wt% or more, more preferably 3 wt% or more with respect to the entire styrene resin.

Moreover, it is preferable that a styrene resin (A) contains the structural unit derived from a vinyl cyanide monomer. The vinyl cyanide monomer is not particularly limited, and specific examples include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like. Of these, acrylonitrile is preferably used. One or more of these can be used. Interlayer adhesion when using a vinyl cyanide monomer such as ABS resin as the thermoplastic resin (B) when using a vinyl cyanide monomer to form a multilayer structure to be described later. This is preferable because of improved properties.
The copolymerization ratio of the vinyl cyanide monomer is determined by the adhesion between layers when a resin containing a vinyl cyanide monomer such as an ABS resin is used as the thermoplastic resin (B) to be described later. From the viewpoint of property, the content is preferably 1 wt% or more, more preferably 5 wt% or more based on the entire styrene resin.

  As the styrene resin (A), a styrene resin containing a structural unit derived from the above-mentioned monomer such as MBS resin is preferable, but in addition to this, styrene mentioned in the thermoplastic resin (B) described later. The above G ′ can also be achieved by mixing an ultra-low molecular weight styrene resin having a weight average molecular weight of about 5000 or less that is compatible with the styrene resin into the resin. However, it is not preferable to add an ultra-low molecular weight resin because the strength of the styrene-based resin (A) may decrease.

  Here, the styrene-based resin (A) preferably has a glass transition temperature (Tg) only in a range of less than 100 ° C. Therefore, the styrene resin (A) may have a plurality of Tg, but all Tg is in the range of less than 100 ° C. and is a styrene resin having no Tg in the range of 100 ° C. or more. Is preferred. As for Tg here, at least one Tg is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 75 ° C. or higher, preferably 98 ° C. or lower, more Preferably it is 95 degrees C or less, More preferably, it is 90 degrees C or less. By being below the upper limit value, it is possible to suppress warping during modeling in the three-dimensional modeling material. Specifically, by setting Tg to the upper limit value or less, the above-described shear storage modulus (G ′) measured at 100 ° C. and 1 Hz can be set to the upper limit value or less. However, since the difference between the temperature solidified after ejection from the nozzle of the 3D printer and the modeling atmosphere temperature becomes small and the amount of shrinkage due to linear expansion after solidification becomes small, it is considered that warpage is suppressed. Moreover, since it is more than a lower limit and the heat resistance of the molded article using the three-dimensional modeling material of this invention improves, it is preferable.

  The styrene resin (A) has a melt index (MI) at 220 ° C. and 10 kg of preferably 10 or more and less than 100, more preferably 20 or more and less than 90. In the properties of the obtained three-dimensional modeling material, it is preferable that it is not less than the above lower limit value because high-speed modeling property during three-dimensional modeling tends to be favorable, and if it is not more than the upper limit value, the molecular weight is not too low. Since there exists a tendency which is excellent in intensity | strength, it is preferable.

  MI of styrene resin (A) can be adjusted with the molecular weight of resin. Although an appropriate molecular weight varies depending on the composition of the resin, the Mw is preferably 50,000 or more and less than 200,000, more preferably 100,000 or more and less than 180,000 if the resin has a preferable composition described later.

(Olefin resin)
The thermoplastic resin (A) used for the three-dimensional modeling material of the present invention can be a resin containing an olefin resin. Here, the olefin resin is a resin having at least a structural unit derived from an alkene, and preferably a resin having a structural unit derived from ethylene, α-olefin, or propylene. Furthermore, you may have the structural unit derived from maleic anhydride, unsaturated carboxylic acid, an acrylate ester monomer, etc. as needed.

  The olefin-based resin is not particularly limited, but can be obtained by a known polymerization method using a known olefin polymerization catalyst using monomers such as propylene, ethylene, and α-olefin. For example, a slurry polymerization method, a solution polymerization method, a gas phase polymerization method, etc. using a multi-site catalyst represented by a Ziegler-Natta type catalyst, a single site catalyst represented by a metallocene catalyst or a post metallocene catalyst, Examples thereof include a bulk polymerization method using a radical initiator.

  The molecular weight of the olefin resin is not limited, but the weight average molecular weight is preferably 20,000 or more, more preferably 50,000 or more, and preferably 1,000,000 or less. The weight average molecular weight here refers to the weight average molecular weight in terms of polystyrene measured by GPC using orthodichlorobenzene or the like as a solvent.

  Specific examples of the olefin resin used for the three-dimensional modeling material of the present invention include, for example, an ultra-low density polyethylene resin, a low density polyethylene resin, a linear low density polyethylene (ethylene-α-olefin copolymer) resin, Examples thereof include medium density polyethylene resins, high density polyethylene resins, homopolymers of propylene, and copolymers with other monomers copolymerizable with propylene. Examples of other monomers copolymerizable with propylene include ethylene, 1-butene, 1-hexene, 4-methyl-pentene-1, 1-octene and other α-olefins having 4 to 12 carbon atoms and divinylbenzene, Examples thereof include dienes such as 1,4-cyclohexadiene, dicyclopentadiene, cyclooctadiene, and ethylidene norbornene. In addition, there is no restriction | limiting in particular in these copolymerization forms (random, a block, etc.), branching, branching degree distribution, and a three-dimensional structure, It can be set as the polymer of an isotactic, atactic, syndiotactic, or these mixed structures. .

In the olefin resin, the thermoplastic resin (A) is selected from monomers so that the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is 1.00 × 10 ⁷ Pa or less. It is preferable to blend a plurality of resins. Among them, from the viewpoint of formability, ultra low density polyethylene resin, low density polyethylene resin, linear low density polyethylene (ethylene-α-olefin copolymer) resin, medium density polyethylene resin, propylene, ethylene and 1-butene. A copolymer with at least one monomer selected from α-olefins having 4 to 12 carbon atoms such as 1-hexene, 4-methyl-pentene-1, and 1-octene is preferable. In particular, considering the heat resistance as a three-dimensional modeling material, it is preferable to select a propylene-based resin as the thermoplastic resin (B) described later, and the interfacial adhesiveness when the core-sheath structure is formed with the propylene-based resin. From the viewpoint, the thermoplastic resin (A) is selected from propylene and α-olefins having 4 to 12 carbon atoms such as ethylene, 1-butene, 1-hexene, 4-methyl-pentene-1, and 1-octene. Copolymers with one or more monomers are preferred. Specific examples of the propylene-based resin include Nippon Polypro Co., Ltd., trade names: Wellnex RMG02 and RFG4VM.

  Here, the olefin resin (A) has a melt index (MI) at 190 ° C. and 10 kg of preferably 10 or more and less than 150, more preferably 20 or more and less than 120. In the properties of the obtained three-dimensional modeling material, it is preferable that it is not less than the above lower limit value because high-speed modeling property during three-dimensional modeling tends to be favorable, and if it is not more than the upper limit value, the molecular weight is not too low. Since there exists a tendency which is excellent in intensity | strength, it is preferable. In addition, MI of olefin resin (A) can be adjusted with the molecular weight of resin.

  Moreover, although melting | fusing point (Tm) of olefin resin (A) is not specifically limited, It is preferable that it is 170 degrees C or less from a relationship with the shear storage elastic modulus (G ') measured at 100 degreeC and 1 Hz. Is 160 ° C. or lower.

[Thermoplastic resin (B)]
The material for three-dimensional modeling of the present invention may contain a thermoplastic resin (B) having a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz of greater than 1.00 × 10 ⁷ Pa, It is preferable to contain a thermoplastic resin (B) in addition to the thermoplastic resin (A) described above. It is preferable to contain the thermoplastic resin (B) because it tends to improve heat resistance that can suppress deformation due to heat during modeling in the three-dimensional modeling material.

(Physical properties)
The thermoplastic resin (B) used for the three-dimensional modeling material of the present invention has a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz, which is greater than 1.00 × 10 ⁷ Pa. From a viewpoint of the heat resistance at the time of modeling and modeling, it is preferably 2.00 × 10 ⁷ Pa or more. In general, the shear storage modulus (G ′) becomes impossible to measure when the resin is solidified. If the measurement is impossible, the shear storage modulus (G ′) greatly exceeds 2.00 × 10 ⁷ Pa. Can be judged.
In this specification, generally known methods can be used as a method for measuring each storage elastic modulus, and it is not particularly limited. Specifically, it is preferable to measure under the conditions described in the examples described later. .

The composition of the thermoplastic resin having the above-mentioned shear storage modulus (G ′) is not particularly limited, as will be described later. For example, the thermoplastic resin is selected from styrene resins, olefin resins, polylactic acid (PLA), and polyester resins. This G ′ can be achieved by appropriately selecting the type of monomer constituting these resins or adding a filler such as carbon fiber or glass fiber.
Especially, it is preferable to select a styrene resin or an olefin resin as a main component from the viewpoint of excellent low moisture absorption and impact resistance. In this case, a main component is a component which occupies 50 wt% or more among thermoplastic resins (B).

The thermoplastic resin (B) used for the three-dimensional modeling material of the present invention has a tensile storage elastic modulus (E ′) measured at 100 ° C. and 10 Hz, from 100 MPa, from the viewpoint of a molded article and heat resistance during modeling. It is preferably large, and more preferably 200 MPa or more. Usually, it is 2000 MPa or less.
The tensile storage modulus (E ′) measured at 100 ° C. and 10 Hz can be adjusted by the resin composition, copolymerization ratio, and the like.

Moreover, the thermoplastic resin (B) used for the three-dimensional modeling material of the present invention has a tensile storage elastic modulus (E ′) measured at 30 ° C. and 10 Hz, and the room temperature of the three-dimensional modeling material and the modeled article obtained. 400 MPa or more is preferable, 800 MPa or more is more preferable, and 1000 MPa or more is more preferable. Usually, it is about 5000 MPa or less.
The tensile storage modulus (E ′) measured at 30 ° C. and 10 Hz can be adjusted by the resin composition, copolymerization ratio, and the like.

(Styrene resin)
The thermoplastic resin (B) used for the three-dimensional modeling material of the present invention can be a resin containing a styrene resin. The styrenic resin can include a structural unit derived from the same monomer as described in detail in the thermoplastic resin (A), and specific examples include, for example, an ABS resin, an AS resin, MBS resin, polystyrene and the like can be mentioned. Among them, ABS resin is preferable because it is excellent in strength and impact resistance. Moreover, it is preferable to select MBS resin from a viewpoint of adhesive strength with styrene-type resin (A) at the time of setting it as the multilayer structure mentioned later.

In the styrenic resin, the thermoplastic resin (B) is selected from monomers such that the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is greater than 1.00 × 10 ⁷ Pa. It is preferable. For example, the styrene resin (B) used as the thermoplastic resin (B) is a specific ABS resin such as HF-3 or EX19C manufactured by UMG ABS, or GT-R-61A manufactured by Denka. Etc.

Here, the styrene resin (B) preferably has a glass transition temperature (Tg) of 100 ° C. or higher. More preferably, it is 101 degreeC or more. Styrenic resin (B) should just have one or more Tg above 100 degreeC, and when it has several Tg, it may have Tg below 100 degreeC.
By being more than a lower limit, the modeling thing of the obtained three-dimensional modeling material and the heat resistance at the time of modeling improve. In particular, when a styrene resin (A) having a low Tg is included, the heat resistance of the three-dimensional modeling material and the modeled product tends to decrease, and therefore, it is preferable to use the styrene resin (B) in combination.

Further, the styrene resin (B) preferably has a melt index (MI) of 10 kg or more at 220 ° C. and 10 kg of 10 or more and less than 100, more preferably 20 or more and less than 90. In the properties of the obtained three-dimensional modeling material, it is preferable that it is not less than the above lower limit value because high-speed modeling property during three-dimensional modeling tends to be favorable, and if it is not more than the upper limit value, the molecular weight is not too low. Since there exists a tendency which is excellent in intensity | strength, it is preferable.
The MI of the styrene resin (B) can be adjusted by the molecular weight of the resin. Although an appropriate molecular weight varies depending on the composition of the resin, the Mw is preferably 50,000 or more and less than 200,000, more preferably 100,000 or more and less than 180,000 if the resin has a preferable composition described later.

The styrene resin (B) used in the three-dimensional modeling material of the present invention has a tensile storage elastic modulus (E ′) measured at 100 ° C. and 10 Hz of 100 MPa or more from the viewpoint of a molded article and heat resistance during modeling. Is preferable, 500 MPa or more is more preferable, and 800 MPa or more is more preferable. Usually, it is about 5000 MPa or less.
The tensile storage modulus (E ′) measured at 100 ° C. and 10 Hz can be adjusted by the resin composition, copolymerization ratio, and the like.

Further, the styrene resin (B) used in the three-dimensional modeling material of the present invention has a tensile storage modulus (E ′) measured at 30 ° C. and 10 Hz, and the room temperature of the three-dimensional modeling material and the modeled article obtained. From the viewpoint of strength at 400, 400 Ma or more is preferable, 800 MPa or more is more preferable, and 1000 MPa or more is more preferable. Usually, it is about 5000 MPa or less.
The tensile storage modulus (E ′) measured at 30 ° C. and 10 Hz can be adjusted by the resin composition, copolymerization ratio, and the like.

(Olefin resin)
The thermoplastic resin (B) used for the three-dimensional modeling material of the present invention can be a resin containing an olefin resin. As an olefin resin, it can contain the structural unit derived from the monomer similar to what was explained in full detail in said thermoplastic resin (A), As an example, an ultra-low density polyethylene resin, Low density polyethylene resin, linear low density polyethylene (ethylene-α-olefin copolymer) resin, medium density polyethylene resin, high density polyethylene resin, propylene homopolymer, other monomers copolymerizable with propylene And the like. Examples of other monomers copolymerizable with propylene include ethylene, 1-butene, 1-hexene, 4-methyl-pentene-1, 1-octene and other α-olefins having 4 to 12 carbon atoms and divinylbenzene, Examples thereof include dienes such as 1,4-cyclohexadiene, dicyclopentadiene, cyclooctadiene, and ethylidene norbornene. In addition, there is no restriction | limiting in particular in these copolymerization forms (random, a block, etc.), branching, branching degree distribution, and a three-dimensional structure, It can be set as the polymer of an isotactic, atactic, syndiotactic, or these mixed structures. .

In the olefin resin, the thermoplastic resin (B) is selected from monomers so that the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is greater than 1.00 × 10 ⁷ Pa. It is preferable to blend a plurality of resins. Among them, from the viewpoint of formability, linear low density polyethylene (ethylene-α-olefin copolymer) resin, medium density polyethylene resin, high density polyethylene resin, propylene homopolymer, propylene, ethylene and 1-butene, A copolymer with one or more monomers selected from α-olefins having 4 to 12 carbon atoms such as 1-hexene, 4-methyl-pentene-1, 1-octene and the like is preferable. In particular, considering the heat resistance as a three-dimensional modeling material, the content of the propylene monomer in the thermoplastic resin (B) is preferably 30 wt% or more, and more preferably 50 wt% or more. In addition, a nucleating agent such as talc may be added to increase crystallinity. Specific propylene-based resins include Nippon Polypro Co., Ltd., trade name: Novatec PP MA3, Wintech WMG03, and the like.

  The molecular weight of the olefin resin is not limited, but the weight average molecular weight is preferably 20,000 or more, more preferably 50,000 or more, and preferably 1,000,000 or less.

  Here, the olefin resin (B) has a melt index (MI) at 190 ° C. and 10 kg of preferably 10 or more and less than 150, more preferably 20 or more and less than 120. In the properties of the obtained three-dimensional modeling material, it is preferable that it is not less than the above lower limit value because high-speed modeling property during three-dimensional modeling tends to be favorable, and if it is not more than the upper limit value, the molecular weight is not too low. Since there exists a tendency which is excellent in intensity | strength, it is preferable. The MI of the olefin resin (B) can be adjusted by the molecular weight of the resin.

  Moreover, although melting | fusing point (Tm) of olefin resin (A) is not specifically limited, It is preferable that it is 120 degreeC or more from a relationship with the shear storage elastic modulus (G ') measured at 100 degreeC and 1 Hz, More preferably Is 130 ° C. or higher and is usually 180 ° C. or lower.

[Composition of 3D modeling material]
The composition of the three-dimensional modeling material of the present invention is not particularly limited, and may be composed only of the above-described thermoplastic resin (A) or may contain other resins. Further, G ′ of the three-dimensional modeling material may be adjusted to a desired range by adding other components to the above-described thermoplastic resin (B).

  When the thermoplastic resin (A) is included, the G ′ of the three-dimensional modeling material can be easily adjusted to a desired range, but a thermoplastic resin ( It is preferable to use either one or both of B) or rubber particles described later. At this time, the thermoplastic resin (A) is preferably 20 wt% or more, more preferably 30 wt% or more with respect to the entire three-dimensional modeling material from the viewpoint of suppressing warpage during modeling. Moreover, 5 wt% or more is preferable with respect to the whole three-dimensional modeling material from a viewpoint of the heat resistance at the time of modeling and modeling, and thermoplastic resin (B) has more preferable 10 wt% or more. Further, the rubber particles are preferably 1 wt% or more, and preferably 2 wt% or more from the viewpoint of heat resistance during modeling. Moreover, from a viewpoint of suppressing a fluid fall, 20 wt% or less is preferable and 10 wt% or less is more preferable.

[Other ingredients]
In addition to the above-described resin, the three-dimensional modeling material of the present invention may contain other components as long as the effects of the present invention are not impaired. The following components may be used in any combination.

(Rubber particles)
Rubber particles may be used for the purpose of improving heat resistance and impact resistance during modeling of the three-dimensional modeling material.
Examples of the rubber particles include acrylic rubber particles, butadiene rubber particles, silicon rubber particles, and olefin rubber particles. In particular, for the purpose of improving the impact resistance of the styrene-based resin and improving the heat resistance during modeling, butadiene-based rubber particles are preferable from the viewpoint of dispersibility in the styrene-based resin. Examples of the butadiene rubber particles include Methrene C-223A manufactured by Mitsubishi Chemical.

(Filler)
For the purpose of improving the rigidity of the three-dimensional modeling material and the filament, it is preferable to use an organic filler or an inorganic filler.
Examples of the organic filler include cellulose fiber, aramid fiber, polyester fiber, polyamide fiber and the like.
Examples of the inorganic filler include carbon fiber, glass fiber, mica, talc, silica, and alumina. Of these, carbon fiber, glass fiber, mica and talc are preferable from the viewpoint of rigidity.

In addition to this, additives such as a flame retardant, an antioxidant, an ultraviolet absorber, and an antiblocking agent may be contained for the purpose of imparting specific characteristics to the three-dimensional modeling material.
Further, other resins may be added as long as the effects of the present invention are not impaired.

[Structure of 3D modeling material]
The form of the three-dimensional modeling material of the present invention is not particularly limited as long as it can be applied to a hot melt lamination type three-dimensional printer. For example, a powder, a pellet, a granule, a filament etc. are mentioned.
In the case of using a plurality of resins, the three-dimensional modeling material of the present invention may be a homogeneous material by mixing a plurality of resins, or by dividing two or more resins to be used into different layers to form a multilayer structure. Good. In particular, in the three-dimensional modeling filament of the present invention, it is preferable to appropriately select whether to use a filament made of a mixed resin or a multi-layered filament according to the desired characteristics.
For example, when the melt adhesion of two or more kinds of resins to be used is low, it is preferable to mix them to obtain a homogeneous three-dimensional modeling material because the strength in the Z-axis direction of the modeled article increases.

In addition, for example, from the viewpoint of heat resistance, cost, and productivity, it is possible to make a multilayer structure using two or more kinds of resins in different layers, and the thermoplastic resin (A) and the thermoplastic resin (B) These are preferably contained in different layers. That is, the shear storage elastic modulus (G ′) measured at 100 ° C. and 1 Hz has a thermoplastic resin (A) of 1.00 × 10 ⁷ Pa or less, and the shear storage elastic modulus (G ′) measured at 100 ° C. and 1 Hz. ) Contains a thermoplastic resin (B) greater than 1.00 × 10 ⁷ Pa, and is a multilayer structure containing the thermoplastic resin (A) and the thermoplastic resin (B) in different layers 3 A three-dimensional modeling material or a three-dimensional modeling filament can be used.

  The multilayer structure is not particularly limited. For example, the multilayer structure in the three-dimensional modeling material of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view of a three-dimensional modeling material. For example, in the case of a three-dimensional modeling filament, an arbitrary section of the filament is cut perpendicularly to the long axis and the cross section is observed. As shown in FIG. 1 (a), a pattern in which two or more kinds of resins have a core-sheath structure, and a pattern in which two or more kinds of resins are sequentially stacked so that the filament cross section has a layer structure as shown in FIG. 1 (b). It is done.

  In the multi-layer structure, the position where each resin is arranged is not particularly limited. However, since the interlayer adhesion of the molded article is excellent, at least a part of the surface of the three-dimensional modeling material contains a thermoplastic resin (A). It is preferable that the thermoplastic resin (A) is contained in the outermost layer. Specifically, it is preferable that 1 occupying most of the surface in FIGS. 1A and 1B is the thermoplastic resin (A).

[3D modeling filament]
The three-dimensional modeling filament of the present invention is manufactured using the above-described three-dimensional modeling material of the present invention. The method for producing the three-dimensional modeling filament of the present invention is not particularly limited, but the method for molding the three-dimensional modeling material used in the present invention, usually by a known molding method such as extrusion molding, or the production of the three-dimensional modeling material. Sometimes, it can be obtained by a method of using the filament as it is. For example, when the three-dimensional modeling filament of the present invention is obtained by extrusion, the conditions are usually 150 to 260 ° C, preferably 170 to 250 ° C.

  The diameter of the three-dimensional modeling filament of the present invention depends on the capacity of the system to be used, but is preferably 1.0 to 5.0 mm, more preferably 1.3 to 3.5 mm. Further, it is preferable that the accuracy of the diameter is within an error of ± 5% with respect to an arbitrary measurement point of the filament from the viewpoint of the stability of the raw material supply.

  In manufacturing a molded body using a hot melt lamination type 3D printer using the 3D modeling filament of the present invention, the 3D modeling filament is stably stored, and the hot melt lamination type 3D printer has 3 A stable supply of the three-dimensional modeling filament is required.

  Therefore, the three-dimensional modeling filament of the present invention is hermetically packaged as a wound body wound around a bobbin, or the wound body is housed in a cartridge for long-term storage, stable feeding, It is preferable from the viewpoint of protection from environmental factors such as moisture and prevention of twisting.

  Examples of the cartridge include a wound body wound around a bobbin, a moisture-proof material or a moisture-absorbing material inside, and a structure in which at least a portion other than an orifice for feeding out the filament is sealed.

  In particular, the moisture content of the three-dimensional modeling filament is preferably 3,000 ppm or less, and more preferably 2,500 ppm or less. The three-dimensional modeling filament product is preferably sealed so that the moisture content of the filament is 3,000 ppm or less, and more preferably 2,500 ppm or less.

  Moreover, in order to prevent the filaments from being blocked (fused) when the three-dimensional modeling filament is used as a wound body, a blocking agent may be applied or coated on the filament surface.

  Examples of the blocking agent that can be used here include silicone-based blocking agents, inorganic fillers such as talc, and fatty acid metal salts. In addition, these blocking agents may be used only by 1 type, and may be used in combination of 2 or more type.

  A preferred form of the filament is a wound body wound around a bobbin or the like, and a cartridge for a three-dimensional printer in which the filament is housed in a container is preferable. In particular, a cartridge in which a wound body of filaments is housed in a container is usually installed in or around a three-dimensional printer, and filaments are always introduced from the cartridge into the three-dimensional printer during molding.

[Method for producing molded article]
A molded body can be produced by molding the three-dimensional modeling material or the three-dimensional modeling filament of the present invention with a hot melt lamination type three-dimensional printer.

  The hot melt lamination type three-dimensional printer generally includes a raw material supply unit such as a heatable substrate (modeling table), an extrusion head (nozzle), a heating melter, a filament guide, and a filament installation unit. Some material extrusion type three-dimensional printers have an extrusion head and a heating / melting device integrated.

  The extrusion head can be arbitrarily moved on the XY plane of the substrate by being installed in the gantry structure. The substrate is a platform for constructing the target 3D object, support material, etc., and heat adhesion and adhesion are obtained with the laminate, and the resulting molded body is used as the desired 3D object to improve dimensional stability. It is preferable that the specifications can be used. In general, at least one of the extrusion head and the substrate is movable in the Z-axis direction perpendicular to the XY plane.

  The raw material is fed out from the raw material supply unit, sent to the extrusion head by a pair of opposed rollers or gears, heated and melted by the extrusion head, and extruded from the tip nozzle. In response to a signal transmitted based on the CAD model, the extrusion head supplies the raw material onto the substrate while moving its position, and deposits the layers. After this step is completed, the stacked deposit is taken out from the substrate, and the support material or the like is peeled off as necessary, or an excess portion is cut off to obtain a molded body as a desired three-dimensional object.

  The means for continuously supplying the raw material to the extrusion head includes a method of feeding and supplying filaments or fibers, a method of supplying powder or granules or pellets from a tank etc. via a quantitative feeder, and a powder or pellets or granules. Examples thereof include a method of extruding and supplying a plasticized material with an extruder or the like. Among these, from the viewpoint of the simplicity of the process and the supply stability, the method of drawing out and supplying the filament, that is, the above-described filament for three-dimensional modeling of the present invention is most preferable.

  When supplying filament raw materials, as described above, it is housed in a cartridge wound in a bobbin shape to ensure stable feeding, protection from environmental factors such as moisture, prevention of twisting and kinking, etc. To preferred.

  When supplying a filament-shaped raw material, it is common to engage a filament with a driving roll such as a nip roll or a gear roll and supply it to the extrusion head while taking it up. Here, in order to stabilize the supply of raw materials by strengthening the grip by engagement between the filament and the drive roll, a minute uneven shape is transferred on the surface of the filament, or the frictional resistance with the engaging portion is reduced. It is also preferable to add an inorganic additive, a spreading agent, a pressure-sensitive adhesive, rubber or the like for enlargement.

  The three-dimensional modeling material used as the filament of the present invention has a temperature of about 180 to 250 ° C. for obtaining fluidity suitable for extrusion, and is applied in comparison with the raw materials conventionally used for molding by a three-dimensional printer. Since the possible temperature range is wide, the temperature of the heating extrusion head is preferably 200 to 240 ° C., and the substrate temperature is usually 110 ° C. or lower, preferably 60 to 80 ° C., and a molded article can be produced stably. .

  The temperature of the molten resin discharged from the extrusion head is preferably 180 ° C or higher, more preferably 190 ° C or higher, on the other hand, preferably 250 ° C or lower, more preferably 240 ° C or lower. .

  When the temperature of the molten resin is equal to or higher than the above lower limit value, the resin flows sufficiently. On the other hand, it is preferable that the temperature of the molten resin is not more than the above upper limit value because it is easy to prevent problems such as thermal decomposition and burning of the resin, smoke generation, odor, stickiness, and lumps.

  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 mm, more preferably 0.02 to 0.8 mm. It is preferable that the molten resin is discharged in such a shape because the CAD model tends to have good reproducibility.

  The three-dimensional modeling material of the present invention is used in a hot melt lamination type three-dimensional printer, but a powder bed melt-bonding type three-dimensional printer is also expected to be effective in suppressing warpage during modeling. The

  The molded product produced by the method for producing a molded product of the present invention is excellent in appearance, strength, heat resistance, post-processability and the like. For this reason, stationery; toys; covers for mobile phones and smartphones; parts such as grips; school teaching materials, home appliances, repair parts for office automation equipment, various parts such as automobiles, motorcycles, bicycles; It can be suitably used for applications such as shaping.

  EXAMPLES Hereinafter, although the content of this invention is demonstrated more concretely using an Example, this invention is not limited by a following example, unless the summary is exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferred values of the upper limit or lower limit in the embodiments of the present invention, and the preferred ranges are the upper limit or lower limit values described above, and It may be a range defined by a combination of values of the examples or values between the examples.

<Method for measuring physical properties>
[Glass transition temperature (Tg)]
Using a differential scanning calorimeter (manufactured by PerkinElmer, Inc., trade name: Diamond DSC), according to JIS K7121, about 10 mg of the sample was heated from 0 ° C. to 250 ° C. at a heating rate of 10 ° C./min. After holding at 250 ° C. for 5 minutes, the temperature was lowered to 0 ° C. at a cooling rate of 10 ° C./min, and the intermediate point glass transition temperature was determined from the thermogram measured when the temperature was raised again to 250 ° C. at a heating rate of 10 ° C./min. The reading was taken as the glass transition temperature (Tg) (° C.).

[Melting point (Tm)]
Using a differential scanning calorimeter (manufactured by PerkinElmer, Inc., trade name: Diamond DSC), according to JIS K7121, about 10 mg of the sample was heated from 0 ° C. to 250 ° C. at a heating rate of 10 ° C./min. After holding at 250 ° C. for 5 minutes, the temperature was lowered to 0 ° C. at a cooling rate of 10 ° C./min, and the melting point (Tm) was read from the thermogram measured when the temperature was raised again to 250 ° C. at a heating rate of 10 ° C./min. It was.

[Tensile storage modulus (E ')]
The raw material pellets and the filaments obtained in the examples and comparative examples were each formed into a sheet having a thickness of about 0.5 mm by hot pressing to obtain a measurement sample. Using a dynamic viscoelasticity measuring device (product name: viscoelastic spectrometer DVA-200, manufactured by IT Measurement Co., Ltd.), vibration frequency: 10 Hz, temperature rising rate: 3 ° C./min, strain 0.1% Then, the storage elastic modulus (E ′) was measured from −100 ° C. to 250 ° C., and from the obtained data, the storage elastic modulus at 100 ° C. (E′100 ° C.) and the storage elastic modulus at 30 ° C. (E′30 ° C).

[Shear storage modulus (G ')]
The filaments obtained in the examples and comparative examples were each formed into a sheet having a thickness of 0.5 mm by hot pressing to obtain a measurement sample. Using a rheometer (manufactured by Thermo Fisher Scientific Co., Ltd., trade name: MARS II), the shear storage modulus (G ′) from 300 ° C. to 80 ° C. at a frequency of 1 Hz and a temperature drop rate of 3 ° C./min. The shear storage elastic modulus (G′100 ° C.) at 100 ° C. was determined from the measured data.

<Formability evaluation method>
[warp]
Using a 3D printer (manufactured by Muto Kogyo Co., Ltd., trade name: MF-2200D), the molding table temperature is 80 ° C., the nozzle temperature is 240 ° C., the molding speed is 30 mm / s, and the internal filling rate is 100%. X A plate having a thickness of 5 mm was formed, the plate formed was placed on a horizontal table, and the formed plate was evaluated according to the following criteria depending on whether or not the plate was lifted from the table.
×: With floating 〇: Without floating

[Heat resistance during molding]
Using the above-mentioned 3D printer, in the modeling table temperature 100 ° C., the nozzle temperature 240 ° C., the modeling speed 100 mm / s, and the automatic container creation mode (the mode in which only the outer wall of the model is spirally stacked and modeled) A cylinder with a diameter of 50 mmφ × height of 60 mm was formed and evaluated according to the following criteria.
×: The shape of the cylinder cannot be maintained by deformation. ○: The shape of the cylinder can be formed while maintaining the shape of the cylinder without being deformed.

〔material〕
<Raw materials>
Styrene resin (A1): manufactured by Denka Co., Ltd., trade name: TH-11, Tg: 86 ° C., Mw: about 160,000, E′100 ° C .: 72 MPa, E′30 ° C .: 2274 MPa, G′100 ° C .: 0.07 × 10 ⁷ Pa, composition (wt%): styrene / butadiene / methyl methacrylate / butyl acrylate = 56/4/35/5
PP resin (A2): manufactured by Nippon Polypro Co., Ltd., trade name: Wellnex RMG02, Tm: 130 ° C., E′100 ° C .: 40 MPa, E′30 ° C .: 430 MPa, G′100 ° C .: 0.002 × 10 ⁷ Pa, composition (wt%) propylene / ethylene = 95/5
PP resin (B1): manufactured by Nippon Polypro Co., Ltd., trade name: Wintech WMG03, Tm: 142 ° C., E′100 ° C .: 300 MPa, E′30 ° C .: 1500 MPa, G′100 ° C .: measurement not possible, composition ( wt%) propylene / ethylene = 98/2
ABS resin (B2): Chi Mei Corp. Product name: PA757H, Tg: 104 ° C., E′100 ° C .: 1219 MPa, E′30 ° C .: 1710 MPa, G′100 ° C .: not measurable

[Example 1]
Using a styrenic resin (A1), a single-screw extruder extrudes from a nozzle with a diameter of 2.5 mm at a melting temperature of 230 to 250 ° C., and then cools in 70 ° C. cooling water to obtain a filament with a diameter of 1.75 mm. Obtained. Table 1 shows each physical property value of the obtained filament and the modeling evaluation result.

[Example 2]
Using PP resin (A2), a single-screw extruder extrudes from a nozzle with a diameter of 2.5 mm at a melting temperature of 180 ° C. to 220 ° C., then cools in 10 ° C. cooling water, and a filament with a diameter of 1.75 mm Got. Table 1 shows each physical property value of the obtained filament and the modeling evaluation result.

[Example 3]
Styrenic resin (A1) and ABS resin (B2) were mixed at a weight ratio of 60/40, kneaded at a temperature of 230 to 250 ° C. with a twin screw extruder, and pelletized. Using this pellet, a filament having a diameter of 1.75 mm was obtained in the same manner as in Example 1. Table 1 shows each physical property value of the obtained filament and the modeling evaluation result.

[Example 4]
Using ABS resin (B2) as the core layer and styrene resin (A1) as the sheath layer, the sheath layer covers the core layer, and the melting temperature is 230 so that the filament diameter: core layer diameter is 2: 1. After co-extrusion at ˜250 ° C., the product was cooled in 70 ° C. cooling water to obtain a filament having a diameter of 1.75 mm. Table 1 shows each physical property value of the obtained filament and the modeling evaluation result.

[Example 5]
Using PP resin (B1) as the core layer and PP resin (A2) as the sheath layer, the sheath layer covers the core layer, and the filament diameter: the diameter of the core layer is 2: 1 Extrusion was performed at a melting temperature of 180 ° C. to 220 ° C. from a nozzle having a diameter of 2.5 mm using an extruder, and then cooled in 10 ° C. cooling water to obtain a filament having a diameter of 1.75 mm. Table 1 shows each physical property value of the obtained filament and the modeling evaluation result.

[Comparative Example 1]
A filament having a diameter of 1.75 mm was obtained using the ABS resin (B2) in the same manner as in Example 1. Table 1 shows each physical property value of the obtained filament and the modeling evaluation result. In addition, G'100 degreeC was solidified at 100 degreeC in this filament, and was not measurable.

[Comparative Example 2]
Using the PP resin (B1), a filament having a diameter of 1.75 mm was obtained in the same manner as in Example 1. Table 1 shows each physical property value of the obtained filament and the modeling evaluation result. In addition, G'100 degreeC was solidified at 100 degreeC in this filament, and was not measurable.

From Table 1, Examples 1-5 contain the thermoplastic resin (A) whose shear storage elastic modulus (G ') measured at 100 degreeC and 1 Hz is 1 * 10 < ⁷ > Pa or less in a filament. Therefore, the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is 1.00 × 10 ⁷ Pa or less, and the warpage of the filament is suppressed.
Examples 3 to 5 include a thermoplastic resin (B) having a shear storage elastic modulus (G ′) measured at 100 ° C. and 1 Hz of greater than 1.0 × 10 ⁷ Pa, and 100 of the filament. Since the shear storage modulus (G ′) measured at 0 ° C. and 1 Hz is larger than 0.09 × 10 ⁷ Pa, the heat resistance during molding is high.

1 Thermoplastic resin (A)
2 Thermoplastic resin (B)

Claims (13)

A material for three-dimensional modeling used in a three-dimensional printer of a hot melt lamination method, wherein the shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is 1.00 × 10 ⁷ Pa or less. 3D modeling material. It is a homogeneous three-dimensional material made of one kind of resin or a mixture of two or more kinds of resins, and has a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz of 0.90. The material for three-dimensional modeling according to claim 1, wherein the material is × 10 ⁷ Pa or less.   The three-dimensional modeling material according to claim 1, which has a multilayer structure in which two or more kinds of resins are used in different layers. The shear storage elastic modulus (G ′) measured at 100 ° C. and 1 Hz contains a thermoplastic resin (A) of 1.00 × 10 ⁷ Pa or less, 3 according to claim 1. Dimensional modeling material. Furthermore, the material for three-dimensional modeling of Claim 4 containing the thermoplastic resin (B) whose shear storage elastic modulus (G ') measured at 100 degreeC and 1 Hz contains more than 1.00 * 10 < ⁷ > Pa. A thermoplastic resin (A) having a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz is 1.00 × 10 ⁷ Pa or less, and a shear storage modulus (G ′) measured at 100 ° C. and 1 Hz. A thermoplastic resin (B) greater than 1.00 × 10 ⁷ Pa, and a multilayer structure containing the thermoplastic resin (A) and the thermoplastic resin (B) in different layers. 3. The three-dimensional modeling material according to 3.   The three-dimensional modeling material according to claim 6, wherein at least a part of the surface of the three-dimensional modeling material is a layer containing the thermoplastic resin (A).   The three-dimensional modeling material according to any one of claims 1 to 7, wherein a tensile storage elastic modulus (E ') measured at 100 ° C and 10 Hz is 100 MPa or more.   A three-dimensional modeling filament comprising the three-dimensional modeling material according to any one of claims 1 to 8, wherein the filament diameter is 1.0 to 5.0 mm.   The three-dimensional modeling filament according to claim 9, wherein the multilayer structure is a core-sheath structure.   The three-dimensional modeling filament according to claim 9 or 10, wherein in the core-sheath structure, 10% or more of the filament diameter is a core part.   The wound body of the filament for three-dimensional modeling of any one of Claims 9-11. The cartridge for three-dimensional printers which accommodated the filament for three-dimensional modeling of any one of Claims 9-11 in the container.

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