JP7336312B2 - THERMOPLASTIC RESIN COMPOSITION, MATERIAL EXTRUSION-TYPE 3D PRINTER-MOLDING FILAMENT, AND METHOD FOR MANUFACTURING MOLDED BODY - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition which is excellent in transparency, heat resistance, and low hygroscopicity, and particularly has good moldability (modelability) by a material extrusion type 3D printer, and a material extrusion type 3D printer molding filament.
The present invention also relates to a filament roll and a material extrusion type three-dimensional printer cartridge. Furthermore, it relates to a method for producing a molded body.

In recent years, three-dimensional printers of various additive manufacturing methods such as a binder injection method, a material extrusion method, and a liquid bath photopolymerization method have been sold. Among them, a three-dimensional printer system based on Material Extrusion (for example, a system manufactured by Stratasys, Inc. in the United States) extrudes a fluid raw material from a nozzle portion provided in an extrusion head to perform computer-assisted printing. It is used to build a three-dimensional object in layers based on a design (CAD) model.

Among them, in the fused deposition modeling method (hereinafter sometimes referred to as “FDM method” (Fused Deposition Modeling method)), first, the raw material is inserted into an extrusion head as a filament made of a thermoplastic resin composition, and heated and melted. while being continuously extruded onto the XY plane substrate in the chamber from the nozzle portion provided in the extrusion head. The extruded resin deposits and fuses onto the already deposited resin laminate, solidifying together as it cools. Due to such a simple system, the FDM method has become widely used.

In a material extrusion three-dimensional printer typified by the FDM method, the nozzle position with respect to the substrate is usually raised in the Z-axis direction perpendicular to the XY plane and the extrusion process is repeated to create a three-dimensional printer similar to a CAD model. A dimensional object is constructed.
Conventionally, raw materials used for extruded filaments generally include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin") and polylactic acid (hereinafter sometimes referred to as "PLA resin"). (Patent Documents 1 to 3).

Japanese Patent Publication No. 2010-521339 JP 2008-194968 A WO2015/037574

However, according to the study of the present inventor, it was found that the above-described prior art has the following problems.
The ABS resin described in Patent Document 1 has a problem that the transparency and moldability (formability) by a material extrusion type three-dimensional printer are not practically sufficient.
The PLA resins described in Patent Documents 2 and 3 have the problem that transparency, moldability (formability) by a material extrusion type three-dimensional printer, and heat resistance are not practically sufficient.
In addition, both ABS resin and PLA resin have high hygroscopicity, and if the moisture-proof treatment is not appropriate, problems such as deterioration of the molded body due to hydrolysis and inclusion of air bubbles generated by hydrolysis occur in the molded body.

In view of the problems of the prior art as described above, the object of the present invention is to provide a thermoplastic resin composition having transparency, low hygroscopicity, heat resistance, and moldability (modelability) by a material extrusion type three-dimensional printer; It is to provide the filament. Another object of the present invention is to provide a method for producing a molded article having excellent shapeability, a filament winding body, and a material extrusion type three-dimensional printer cartridge.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that a filament for material extrusion type three-dimensional printer molding made of a thermoplastic resin composition containing a specific cyclic polyolefin and a hydrocarbon rubber softener is the above problem. can be solved.
That is, the present invention has the following features.

[1] A thermoplastic resin composition containing a cyclic polyolefin (A) and a hydrocarbon rubber softener (B), wherein the cyclic polyolefin (A) contains at least one aromatic vinyl monomer unit and a hydrogenated block copolymer which is a hydrogenation of a block copolymer comprising at least one conjugated diene monomer unit, the hydrogenated block copolymer being hydrogen which is a hydrogenation of a polymer block comprising the aromatic vinyl monomer unit and a hydrogenated conjugated diene polymer block unit which is a hydrogenated polymer block composed of the conjugated diene monomer unit, and the hydrogenated block copolymer comprises the hydrogenated aromatic vinyl polymer block. A thermoplastic resin composition having at least two units and having at least one hydrogenated conjugated diene polymer block unit.

[2] The thermoplastic resin composition according to [1], which contains 1 to 100 parts by mass of the softener for hydrocarbon rubber (B) with respect to 100 parts by mass of the cyclic polyolefin (A).
[3] the hydrogenated aromatic vinyl polymer block units have a hydrogenation level of 90% or more, and the hydrogenated conjugated diene polymer block units have a hydrogenation level of 95% or more, [1] or [2] ] The thermoplastic resin composition according to .
[4] Any one of [1] to [3], wherein the hydrogenated aromatic vinyl polymer block unit is composed of hydrogenated polystyrene, and the content in the cyclic polyolefin (A) is 30 to 99 mol%. The thermoplastic resin composition according to .

[5] Any one of [1] to [4], wherein the hydrogenated conjugated diene polymer block unit is composed of hydrogenated polybutadiene, and the content in the cyclic polyolefin (A) is 1 to 70 mol%. The thermoplastic resin composition described.
[6] A filament made of the thermoplastic resin composition according to any one of [1] to [5].
[7] The filament according to [6], which is a filament for material extrusion type three-dimensional printer molding.
[8] A wound filament comprising the filament according to [6] or [7].
[9] A material-extrusion type three-dimensional printer cartridge containing the filament described in [7] in a container.
[10] A method for producing a molded article, wherein the filament according to [7] is used to obtain a molded article by a material extrusion three-dimensional printer.

According to the present invention, a thermoplastic resin composition having excellent transparency, low hygroscopicity, heat resistance, and moldability (formability) by a material extrusion type 3D printer and a material extrusion type 3D printer molding filament are provided. be. In addition, it is possible to provide a method for producing a molded article having good moldability (modelability) by a material extrusion type three-dimensional printer.

(a) Side view, (b) Top view of object 1 (vase) to be modeled in the modelability test (a) Side view, (b) rear view of Model 2 (ship) to be modeled in the modelability test (a) Front view and (b) top view of model 2 (ship) in FIG.

The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description content as long as it does not exceed the gist of the present invention. Arbitrary modifications can be made without departing from the gist of the invention.
In the following, when a numerical value or physical property value is sandwiched before and after the "~", it is used to include the values before and after it.

The invention according to the present application relates to a thermoplastic resin composition containing a cyclic polyolefin (A) and a hydrocarbon-based rubber softening agent (B), particularly a material extrusion type three-dimensional printer molding comprising the thermoplastic resin composition It is an invention about filaments.

<Cyclic polyolefin (A)>
The cyclic polyolefin (A) of the present invention comprises a hydrogenated block copolymer which is a hydrogenated block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit.
The hydrogenated block copolymer includes hydrogenated aromatic vinyl polymer block units that are hydrogenated polymer blocks composed of the aromatic vinyl monomer units, and hydrogen that is hydrogenated polymer blocks composed of the conjugated diene monomer units. conjugated diene polymer block units.
The hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit.

The cyclic polyolefin (A) of the present invention preferably comprises the above hydrogenated block copolymer from the viewpoint of transparency and weather resistance.
As used herein, "block" refers to polymerized segments of a copolymer that represent microlayer separation from structurally or compositionally distinct polymerized segments of the copolymer, as described below. Thus, for example, "having at least two block units" means having at least two polymerized segments of the copolymer representing microlayer separation from structurally or compositionally distinct polymerized segments in the hydrogenated block copolymer. Say things.

The aromatic vinyl monomer, which is the starting material for the aromatic vinyl monomer unit, is a monomer represented by the following general formula (1).

Here, R is hydrogen or an alkyl group, and Ar is a phenyl group, halophenyl group, alkylphenyl group, alkylhalophenyl group, naphthyl group, pyridinyl group, or anthracenyl group.

The alkyl group may be a mono- or multiply substituted alkyl group with functional groups such as halo, nitro, amino, hydroxy, cyano, carbonyl and carboxyl groups. Also, the number of carbon atoms in the alkyl group is preferably 1 to 6.
Moreover, said Ar is preferably a phenyl group or an alkylphenyl group, more preferably a phenyl group.

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

The conjugated diene monomer, which is the starting material for the conjugated diene monomer unit, is not particularly limited as long as it is a monomer having two conjugated double bonds.
Conjugated diene monomers include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3 pentadiene and analogs thereof, and mixtures thereof.

The polybutadiene, which is a polymer of 1,3-butadiene, has either a 1,2 configuration that gives the equivalent of 1-butene repeating units when hydrogenated, or a 1,4 configuration that gives the equivalent of ethylene repeating units when hydrogenated. can include

Hydrogenated polymerizable blocks composed of the above aromatic vinyl monomers and the above conjugated diene monomers including 1,3-butadiene are included in the hydrogenated block copolymers used in the present invention. Preferably, the hydrogenated block copolymer is a block copolymer without functional groups.
Note that "free of functional groups" means that no functional groups, ie groups containing elements other than carbon and hydrogen, are present in the block copolymer.

A preferred example of the hydrogenated aromatic vinyl polymer block unit is hydrogenated polystyrene, and a preferred example of the hydrogenated conjugated diene polymer block unit is hydrogenated polybutadiene.
And one preferred embodiment of the hydrogenated block copolymer can include hydrogenated triblock or pentablock copolymers of styrene and butadiene, preferably without any other functional groups or structural modifiers.
A "block" is defined as a polymerized segment of a copolymer that represents a microlayer separation from structurally or compositionally distinct polymerized segments of the copolymer. Microlayer separation results from the immiscibility of the polymerized segments in the block copolymer.
Microlayer separation and block copolymers are extensively discussed in PHYSICS TODAY, February 1999, pp. 32-38, "Block Copolymers-Designer Soft Materials".

The content of hydrogenated aromatic vinyl polymer block units is preferably 30 to 99 mol %, more preferably 40 to 90 mol %, relative to the cyclic polyolefin (A).
If the ratio of the hydrogenated aromatic vinyl polymer block units is at least the above lower limit, the rigidity will not decrease, and if it is below the above upper limit, the brittleness will not be aggravated.

The content of hydrogenated conjugated diene polymer block units is preferably 1 to 70 mol %, more preferably 10 to 60 mol %, relative to the cyclic polyolefin (A).
If the ratio of the hydrogenated conjugated diene polymer block units is at least the above lower limit, the brittleness will not be aggravated, and if it is at or below the above upper limit, the rigidity will not be reduced.

As described above, the polyolefin according to the present invention is a "cyclic polyolefin", and this "cyclic" means an alicyclic ring produced by hydrogenation of the aromatic ring of the hydrogenated aromatic vinyl polymer block unit. Refers to formula structures.

The hydrogenated block copolymers of the present invention are triblock, multiblock, tapered block such as SBS, SBSBS, SIS, SISIS, and SISBS (wherein S is polystyrene, B is polybutadiene, and I is polyisoprene). , and star block copolymers.

The hydrogenated block copolymers of the present invention contain segments of aromatic vinyl polymer at each end. Thus, the hydrogenated block copolymers of the present invention will have at least two hydrogenated aromatic vinyl polymer block units. At least one hydrogenated conjugated diene polymer block unit is present between the two hydrogenated aromatic vinyl polymer block units.

The pre-hydrogenated block copolymer that makes up said hydrogenated block copolymer may contain a number of additional blocks, and these blocks may be attached at any position on the triblock polymer backbone. Thus, linear blocks include, for example, SBS, SBSB, SBSBS, and SBSBSB. The copolymer may be branched and the polymer chains 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, even more preferably 45,000 or more, and particularly preferably 50,000 or more. In addition, the upper limit of Mw 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, most preferably 85,000 or less, extremely preferably 80 , 000 or less.
If Mw is at least the above lower limit, the mechanical strength does not decrease, and if it is at most the above upper limit, moldability does not deteriorate.
Mw herein is determined using gel permeation chromatography (GPC).

The hydrogenation level of the hydrogenated block copolymer is preferably 90% or more hydrogenated aromatic vinyl polymer block units and 95% or more hydrogenated conjugated diene polymer block units, more preferably hydrogenated aromatic vinyl polymer block units. is 95% or more, hydrogenated conjugated diene polymer block units are 99% or more, more preferably hydrogenated aromatic vinyl polymer block units are 98% or more, and hydrogenated conjugated diene polymer block units are 99.5% or more. Particularly preferably, the hydrogenated aromatic vinyl polymer block units are 99.5% or more, and the hydrogenated conjugated diene polymer block units are 99.5% or more.
Incidentally, the hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the ratio at which the aromatic vinyl polymer block unit is saturated by hydrogenation, and the hydrogenation level of the hydrogenated conjugated diene polymer block unit indicates the Indicates the percentage of polymer block units saturated by hydrogenation. Such high levels of hydrogenation are preferred for heat resistance and transparency.

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

Although the melt flow rate (MFR) of the cyclic polyolefin (A) of the present invention is not particularly limited, it is usually 0.1 g/10 min or more, and from the viewpoint of the molding method and appearance of the molded product, preferably 0.2 g/10 minutes or more. Further, it is usually 200 g/10 minutes or less, preferably 100 g/10 minutes or less, more preferably 50 g/10 minutes or less from the viewpoint of material strength.
MFR was measured according to ISO 1133 under conditions of a measurement temperature of 230°C and a measurement load of 2.16 kg.

The cyclic polyolefins (A) may be used singly or in combination of two or more having different monomer unit compositions, physical properties, and the like.
A commercially available product can be used as the cyclic polyolefin (A) of the present invention. Specifically, Mitsubishi Chemical Corporation: Zelas (registered trademark) can be mentioned.

<Softening agent for hydrocarbon rubber (B)>
The hydrocarbon rubber softener (B) used in the present invention softens the cyclic polyolefin (A) and contributes to improving the flexibility, elasticity, workability and fluidity of the thermoplastic resin composition.
Examples of the softener for hydrocarbon rubber (B) include mineral oil softeners and synthetic resin softeners, but mineral oil softeners are preferred from the viewpoint of affinity with the cyclic polyolefin (A).

Mineral oil softeners are generally mixtures of aromatic, naphthenic and paraffinic hydrocarbons, paraffinic oils having at least 50% of the total carbon atoms being paraffinic hydrocarbons. , those in which 30 to 45% of the total carbon atoms are naphthenic hydrocarbons are called naphthenic oils, and those in which 35% or more of the total carbon atoms are aromatic hydrocarbons are called aromatic oils. Among these, paraffinic oils are preferably used in the present invention.
In addition, one kind of softening agent for hydrocarbon rubber may be used alone, or two or more kinds thereof may be used in combination.

The kinematic viscosity at 40° C. of the softener for hydrocarbon rubber (B) is preferably 20 centistokes or more, more preferably 50 centistokes or more, and is preferably 800 centistokes or less, more preferably 600 centistokes. It is below.
The flash point (COC method) of the softener for hydrocarbon-based rubber (B) is preferably 200° C. or higher, more preferably 250° C. or higher.

The hydrocarbon-based rubber softening agent (B) can be obtained as a commercial item.
Examples of applicable commercial products include "Nisseki Polybutene (registered trademark) HV" series manufactured by JX Nippon Oil & Energy Co., Ltd., and Diana (registered trademark) "Process Oil PW" series manufactured by Idemitsu Kosan. Applicable products can be appropriately selected and used from

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains a cyclic polyolefin (A) and a hydrocarbon rubber softener (B).
The thermoplastic resin composition of the present invention preferably contains 1 to 100 parts by mass of the softener for hydrocarbon rubber (B) with respect to 100 parts by mass of the cyclic polyolefin (A).

The content of the hydrocarbon-based rubber softening agent (B) is more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more. Moreover, 75 mass parts or less are more preferable, and 50 mass parts or less are still more preferable.
If the content of the softener for hydrocarbon-based rubber (B) is within the above range, moldability (formability) by a material extrusion type three-dimensional printer will be good.

The MFR of the thermoplastic resin composition is preferably 10 to 1000 g/10 minutes, more preferably 20 to 500 g/10 minutes, even more preferably 50 to 300 g/10 minutes.
Also, the Vicat softening temperature is preferably 60° C. or higher, more preferably 70° C. or higher, and even more preferably 80° C. or higher.
Also, the haze is preferably 2.0 or less, more preferably 1.0 or less.
Also, the water absorption is preferably 0.1% or less, more preferably 0.05% or less.

<Other ingredients>
Other components can be added to the thermoplastic resin composition of the present invention as long as the effects of the present invention are not impaired.
Other components include, for example, other resins, rubbers, additives or fillers.

The other resins are resins other than the component (A), and examples include polypropylene resins, polyethylene resins, polyester resins, polyamide resins, styrene resins, acrylic resins, polycarbonate resins, polyvinyl chloride resins, and various elastomers. mentioned.
These may be used individually by 1 type, and may use 2 or more types together.
The content of the other resins is 50% by mass or less, preferably 30% by mass or less, of the total components.

Examples of the additives include antioxidants, acidic compounds and derivatives thereof, lubricants, ultraviolet absorbers, light stabilizers, nucleating agents, flame retardants, impact modifiers, foaming agents, coloring agents, organic peroxides, material extrusion type Inorganic additives, spreading agents, adhesives and the like for increasing the frictional resistance between the filament and the engaging portion during molding by a three-dimensional printer.
These may be used individually by 1 type, and may use 2 or more types together.

Examples of the filler include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, and glass cut fiber. , glass milled fiber, glass flake, glass powder, silicon carbide, silicon nitride, gypsum, gypsum whisker, calcined kaolin, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, metal powder, Inorganic fillers such as ceramic whiskers, potassium titanate, boron nitride, graphite or carbon fibers; Organic fillers such as naturally derived polymers such as starch, cellulose fine particles, wood flour, bean curd refuse, rice husks, bran, or modified products thereof materials.
These may be used individually by 1 type, and may use 2 or more types together.
The filler content is 50% by mass or less, preferably 30% by mass or less, of the total components.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition of the present invention is prepared by mixing components (A) and (B) and, if necessary, other components with a conventional extruder, Banbury mixer, roll, Brabender plastograph, kneader Brabender, or the like. It can be produced by kneading in a conventional manner.
Among these manufacturing methods, it is preferable to use an extruder, particularly a twin-screw extruder.

When the thermoplastic resin composition of the present invention is produced by kneading with an extruder or the like, it can be produced by melt-kneading in a state of being heated to generally 180 to 300°C, preferably 220 to 280°C.

<Filament for material extrusion type 3D printer molding>
The material extrusion type three-dimensional printer forming filament (hereinafter sometimes referred to as "filament") of the present invention comprises the thermoplastic resin composition of the present invention.
The filament can be produced by molding the thermoplastic resin composition of the present invention by a known molding method such as extrusion molding, or by directly forming a filament during the production of the thermoplastic resin composition. .
For example, when filaments are obtained by extrusion molding, the conditions are usually 150 to 300°C, preferably 180 to 280°C.

The diameter of the filament is preferably 1.0-5.0 mm, more preferably 1.3-3.5 mm, depending on the capacity of the system used.
From the viewpoint of stability of raw material supply, it is preferable that the accuracy of the diameter is within ±5% with respect to an arbitrary measurement point of the filament.

In producing a molded article using the filament with a material extrusion three-dimensional printer, it is required to stably store the filament and to stably supply the filament to the material extrusion three dimensional printer.
Therefore, the material extrusion type three-dimensional printer molding filament of the present invention is hermetically packaged as a wound body wound on a bobbin, or this wound body is housed in a cartridge, so that it can be stored for a long time. It is preferable from the viewpoints of stable delivery, protection from environmental factors such as humidity, prevention of twisting, and the like.
Examples of the cartridge include a wound body wound around a bobbin, and a structure in which a moisture-proof material or a moisture-absorbing material is used inside and at least the part other than the orifice through which the filament is delivered is sealed.

In particular, the moisture content of the filament for material extrusion type three-dimensional printer molding is preferably 0.1% or less, more preferably 0.05% or less.

If blocking (fusion) occurs between the filaments when the filaments are wound, the surface of the filaments may be coated or coated with a blocking agent.
Examples of the blocking agent include silicone-based blocking agents, inorganic fillers such as talc, and fatty acid metal salts. These may be used individually by 1 type, and may use 2 or more types together.

A preferable form of the filament is a wound body wound around a bobbin or the like, and a cartridge for a material extrusion type three-dimensional printer containing the filament in a container is preferable. In particular, the cartridge containing the wound body of the filament in the container is usually installed in or around the material extrusion type three-dimensional printer, and the filament is constantly introduced from the cartridge into the material extrusion type three-dimensional printer during molding.

<Method for manufacturing molded body>
The method for producing a molded article of the present invention is characterized by using a filament made of the thermoplastic resin composition of the present invention as a raw material and molding the raw material with a material extrusion type three-dimensional printer.

A material extrusion type three-dimensional printer generally includes a material supply unit such as a heatable substrate, an extrusion head, a heat melter, a filament guide, and a filament installation unit. Some material extrusion type three-dimensional printers have an extrusion head and a heat melter integrated.

The extrusion head can be arbitrarily moved on the XY plane of the substrate by being installed on the gantry structure. A substrate is a platform for constructing a desired three-dimensional object or support material, etc., and by heating and retaining heat, adhesion to a laminate can be obtained, and the dimensional stability of the obtained molded product can be improved as a desired three-dimensional object. It is preferable to have a specification that can be At least one of the extrusion head and the substrate is usually movable in the Z-axis direction perpendicular to the XY plane.

The filament is drawn out from a raw material supply section, sent to an extrusion head by a set of opposing rollers or gears, heated and melted in the extrusion head, and extruded from a tip nozzle.
Based on the CAD model, the signal sent from the extrusion head moves the position of the extrusion head to supply the raw material onto the substrate and deposit it in layers. After this step is completed, the laminated deposit is taken out from the substrate, and if necessary, the supporting material or the like is peeled off, or excess portions are cut off, thereby obtaining a molded body as a desired three-dimensional object.

When supplying the filament, as described above, it is preferable that the wound body wound around a bobbin or the like is stored in the cartridge from the viewpoint of stable feeding, protection from environmental factors such as moisture, and prevention of twisting. preferable.

When supplying the filament, it is common to engage the filament with a drive roll such as a nip roll or a gear roll, and feed the filament to the extrusion head while taking it off.
Here, in order to stabilize the raw material supply by making the gripping by the engagement between the filament and the driving roll stronger, the fine uneven shape is transferred to the surface of the filament, or the frictional resistance with the engaging part is reduced. It is also preferable to add an inorganic additive, a spreading agent, an adhesive, a rubber, or the like to increase the size.

The cyclic polyolefin used as the filament of the present invention has a temperature of about 180 to 270 ° C. to obtain suitable fluidity for extrusion, which is an applicable temperature compared to raw materials conventionally used for molding with a three-dimensional printer. Large area.
In the production method of the present invention, the temperature of the heating extrusion head is set at 180 to 220.degree. C. and the substrate temperature is set at 80.degree. C. or lower, preferably 60 to 70.degree.

The temperature of the molten resin discharged from the extrusion head is preferably 180°C or higher, more preferably 190°C or higher. Moreover, 270 degrees C or less is preferable and 240 degrees C or less is more preferable.
If the temperature of the molten resin is at least the above lower limit, it is preferable for extruding a resin with high heat resistance. It is also preferable from the viewpoint of preventing deterioration. On the other hand, if it is less than the above upper limit, it is preferable because it is easy to prevent the occurrence of defects such as thermal decomposition, burning, smoke, odor, and stickiness of the resin, and it becomes possible to discharge at high speed, improving modeling efficiency.

The molten resin extruded from the extrusion head is preferably in the form of strands with a diameter of 0.01 to 1 mm, more preferably 0.02 to 0.8 mm. When the molten resin is discharged in such a shape, the reproducibility of the CAD model is improved, which is preferable.

<Molded body>
The molded article of the present invention is excellent in soft texture, heat resistance and the like. For this reason, stationery; toys; covers for mobile phones and smartphones; parts such as grips; It can be suitably used for the purpose.

EXAMPLES The content of the present invention will be described in more detail below using examples, but the present invention is not limited by the following examples as long as the gist thereof is not exceeded. Various production conditions and values of evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention. It may be a range defined by the value of the example or a combination of the values of the examples.

[Physical properties]
<Polymer block ratio>
[Measurement by carbon NMR]
・ Apparatus: "AVANCE 400 spectrometer" manufactured by Bruker
・Solvent: ortho-dichlorobenzene-h ₄ /para-dichlorobenzene-d ₄ mixed solvent ・Concentration: 0.3 g/2.5 mL
・Measurement: ¹³ C-NMR
・Resonant frequency: 400MHz
・Accumulation count: 1536
・Flip angle: 45 degrees ・Data acquisition time: 1.5 seconds ・Pulse repetition time: 15 seconds ・Measurement temperature: 100°C
・¹ H irradiation: complete decoupling

<Hydrogenation level of hydrogenated aromatic vinyl polymer block unit and hydrogenated conjugated diene polymer block unit>
[Measurement by proton NMR]
・ Apparatus: "400YH spectrometer" manufactured by JASCO Corporation
・Solvent: heavy chloroform ・Concentration: 0.045 g/1.0 mL
・Measurement: ¹ H-NMR
・Resonance frequency: 400MHz
・Accumulation times: 8
・Measurement temperature: 18.5°C
・Hydrogenation level of hydrogenated aromatic vinyl polymer block units: integral value reduction rate of 6.8 to 7.5 ppm ・Hydrogenation level of hydrogenated conjugated diene polymer block units: integral value reduction of 5.7 to 6.4 ppm rate

<Melt flow rate (MFR)>
Using the obtained thermoplastic example resin composition, in accordance with ISO 1133, at a temperature of 230 ° C. and a load of 2.16 kg, the index of filament formability and formability (formability) by a material extrusion type three-dimensional printer A certain MFR was measured.
・Equipment: "Melt Indexer" manufactured by Toyo Seiki Seisakusho Co., Ltd.
・Orifice hole diameter: 2mm

<Vicat softening temperature>
Using the obtained thermoplastic resin composition, an in-line screw type injection molding machine ("J110AD" manufactured by JSW) was used at an injection pressure of 50 MPa, a cylinder temperature of 250 ° C., and a mold temperature of 50 ° C. to obtain a thickness of 4 mm x width. A 10 mm x 80 mm long test piece was molded.
Using this test piece, the Vicat softening temperature, which is an index of heat resistance, was measured at a heating rate of 50° C./h and a load of 10 N according to ISO306.

<Haze>
Using the obtained thermoplastic example resin composition, an in-line screw type injection molding machine (manufactured by JSW "J110AD") was used at an injection pressure of 50 MPa, a cylinder temperature of 250 ° C., and a mold temperature of 50 ° C. to obtain a thickness of 2 mm × A test piece having a width of 100 mm and a length of 100 mm was molded.
Using this test piece, haze, which is an index of transparency, was measured according to ISO 14782.

<Water absorption rate>
Using the obtained thermoplastic example resin composition, the water absorption, which is an index of low hygroscopicity, was measured at 180° C. in accordance with ISO 760.
When the water absorption is 0.01% or less, it is <0.01%.

<Filament formability>
Using the obtained thermoplastic resin composition (pellet form), extrusion molding is performed in the range of 185 to 225 ° C. with a single screw extruder (Φ30 mm), and a material extrusion type three-dimensional printer with a cross-sectional diameter of 1.75 mm A forming filament was produced.
When the filament could be formed, the filament formability was evaluated as "○".
When the filament could not be formed due to extrusion torque overload, the filament formability was evaluated as "x".

<Formability>
Using the obtained filament, using "H480-2" manufactured by AFINIA as an extrusion lamination deposition system by the hot melt lamination method, a modeled object 1 (vase: Fig. 1 (a) (b)) is used as a three-dimensional object. And molded object 2 (ship: FIGS. 2(a) and 2(b), FIGS. 3(a) and 3(b)) was molded.
The molding conditions were PLA conditions (nozzle temperature 200 to 220° C., platform temperature 50° C.), FINE mode, lamination pitch 0.25 mm.
The moldability in this molding was evaluated according to the following criteria.
◯: Beautifully formed.
x: Sufficient discharge was not obtained, and modeling was not possible.

[material]
<Cyclic polyolefin (A-1)>
"Xerus (registered trademark) MC930" manufactured by Mitsubishi Chemical Corporation
・ Density (ASTM D792): 0.94 g/cm ³
・MFR (230°C, 2.16 kg): 1 g/10 minutes ・Hydrogenated aromatic vinyl polymer block unit: Hydrogenated polystyrene/hydrogenated conjugated diene polymer block with a hydrogenation level of 99.5% or more at a content of 67 mol% Unit: content 33 mol%, hydrogenated polybutadiene with hydrogenation level of 99.5% or more Block structure: pentablock structure, total hydrogenation level: 99.5% or more Glass transition temperature: 129°C

<Softening agent for hydrocarbon rubber (B-1)>
Diana (registered trademark) process oil PW90 manufactured by Idemitsu Kosan Co., Ltd. [paraffin oil, kinematic viscosity (40 ° C.): 90 centistokes, flash point (COC method): 266 ° C.]

<Polylactic acid (X-1)>
ingeo4032D PLA (polylactic acid resin) manufactured by NatureWorks
・ Density (ISO 1183): 1.24 g/cm ³
・MFR (230°C, load 2.16 kg): 12 g/10 minutes ・Mw: 200,000

[Example 1]
100 parts by mass of component (A-1) and 20 parts by mass of component (B-1) are extruded at a speed of 12 kg/h with a co-directional twin-screw extruder (TEM26SS Φ26 mm, L/D = 48.5 manufactured by Toshiba Machine Co., Ltd.). and melt-kneaded by raising the temperature in the range of 240° C. to produce a thermoplastic resin composition.
Evaluation was performed using the obtained pellets. Table 1 shows the results.

[Comparative Example 1]
Evaluation was performed in the same manner as in Example 1 except that polylactic acid (X-1), which is a resin other than the cyclic polyolefin (A), was used as a raw material. Table 1 shows the results.

From Table 1, it can be seen that Example 1 corresponding to the present invention has good heat resistance, transparency, low hygroscopicity, and moldability (formability) by a material extrusion type three-dimensional printer.
In contrast, Comparative Example 1, which does not correspond to the present invention, was poor in heat resistance, transparency, and low hygroscopicity. Regarding the moldability (formability) by the material extrusion type three-dimensional printer, the object 1 with a simple shape could be formed, but the object 2 with a complicated shape could not be formed.

According to the present invention, it is possible to obtain a thermoplastic resin composition having excellent transparency, low hygroscopicity, heat resistance, and moldability (formability) by a material extrusion type three-dimensional printer, and a filament for three-dimensional printer molding. In addition, it is possible to provide a method for producing a molded article having good moldability (modelability) by a material extrusion type three-dimensional printer.

Claims (6)

A thermoplastic resin composition containing a cyclic polyolefin (A) and a hydrocarbon rubber softener (B),
Containing 1 to 100 parts by mass of the softener for hydrocarbon rubber (B) with respect to 100 parts by mass of the cyclic polyolefin (A),
The cyclic polyolefin (A) consists of a hydrogenated block copolymer which is a hydrogenated block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit,
The hydrogenated block copolymer includes hydrogenated aromatic vinyl polymer block units, which are hydrogenated polymer blocks composed of the aromatic vinyl monomer units, and hydrogenated polymer blocks, which are hydrogenated polymer blocks composed of the conjugated diene monomer units. having a conjugated diene polymer block unit,
the hydrogenated block copolymer has at least two of said hydrogenated aromatic vinyl polymer block units and at least one of said hydrogenated conjugated diene polymer block units ;
the hydrogenated aromatic vinyl polymer block units have a hydrogenation level of 90% or greater, and the hydrogenated conjugated diene polymer block units have a hydrogenation level of 95% or greater;
The hydrogenated aromatic vinyl polymer block unit is composed of hydrogenated polystyrene, and the content in the cyclic polyolefin (A) is 30 to 99 mol%,
The thermoplastic resin composition, wherein the hydrogenated conjugated diene polymer block unit consists of hydrogenated polybutadiene, and the content in the cyclic polyolefin (A) is 1 to 70 mol %. A filament made of the thermoplastic resin composition according to claim 1 . 3. The filament according to claim 2 , which is a filament for material extrusion type three-dimensional printer molding. A wound filament comprising the filament according to claim 2 or 3 . A cartridge for a material extrusion type three-dimensional printer, wherein the filament according to claim 3 is stored in a container. 4. A method for producing a molded article, wherein the filament according to claim 3 is used to obtain a molded article by a material extrusion type three-dimensional printer.