JP6940498B2 - Manufacturing materials for 3D printers and 3D objects - Google Patents

Description

An embodiment of the present invention relates to a modeling material used in a fused deposition modeling 3D printer and a method for manufacturing a three-dimensional object using the same.

In recent years, 3D printers capable of modeling a modeling material such as resin into a desired three-dimensional three-dimensional shape have become widespread. A 3D printer is a type of rapid prototyping (three-dimensional modeling machine), and is a three-dimensional printer that creates a three-dimensional shape with a predetermined modeling material based on 3D data created on a computer such as a PC.

As such a 3D printer, for example, a fused deposition modeling method (see, for example, Japanese Patent Application Laid-Open No. 2014-516829) in which a three-dimensional shape is produced by melting and laminating a thermoplastic resin at a high temperature is known.

As the modeling material used in the above-mentioned heat-melt lamination method, acrylonitrile-butadiene-styrene copolymer (hereinafter, referred to as "ABS resin"), polylactic acid resin (hereinafter, referred to as "PLA resin") and the like are generally used. used.
Further, Japanese Patent Application Laid-Open No. 2016-60147 proposes a molding material for a 3D printer of a hot melt lamination method containing a cyclic polyolefin resin.

Japanese Patent Publication No. 2014-516829 Japanese Unexamined Patent Publication No. 2016-60147

The cyclic olefin resin has the advantages that the modeled product is less deformed and has excellent transparency and surface treatment (polishing and coating) properties.
However, when a cyclic olefin resin is used as a molding material for a 3D printer in a fused deposition modeling method, it may be difficult for the molten resin to follow the movement of the printer head due to the high viscosity of the molten resin, and it may be difficult to increase the molding speed. I understand.

Therefore, it is an object of the present invention to provide a modeling material used for a fused deposition modeling 3D printer, which can improve the modeling speed, and a method for manufacturing a three-dimensional object. And.

An embodiment of the present invention is a modeling material used for a fused deposition modeling 3D printer, which comprises a cyclic olefin resin and at least one selected from the group consisting of a terpene resin and a petroleum resin. Regarding.

Another embodiment of the present invention relates to a method for manufacturing a three-dimensional object, which comprises modeling a three-dimensional object with a fused deposition modeling 3D printer using the above-mentioned modeling material.

According to the embodiment of the present invention, it is possible to provide a modeling material used for a 3D printer of a hot melt lamination method, which enables an improvement in a modeling speed, and a method for manufacturing a three-dimensional object. ..

Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

1. 1. Modeling Material The modeling material used in the Fused Deposition Modeling 3D printer of the embodiment of the present invention (hereinafter, may also be referred to as "modeling material for 3D printer" or "modeling material") is a cyclic olefin resin. Includes at least one selected from the group consisting of terpene resins and petroleum resins.

The modeling material of this embodiment contains a cyclic olefin resin.
ABS resin, PLA resin, etc. are generally used as the molding material used in the Fused Deposition Modeling method, but ABS resin has problems such as large thermal deformation during molding and strong odor. , ABS resin shaped products are prone to warp deformation, and it is necessary to take measures such as heating the molding table to reduce it. Further, the molded product made of PLA resin has problems such as low heat resistance and some difficulty in paintability. Further, both the ABS resin and the PLA resin have low transparency, and there are restrictions when trying to produce a modeled product having high transparency. In order to obtain a highly transparent model, it is conceivable to use a polycarbonate resin or a polymethylmethacrylate resin, but these require a special device for heat retention during modeling.

On the other hand, the general characteristics of cyclic olefin resins include excellent transparency, easy control of heat resistant temperature, less deformation, less residual metals, monomers, oligomers (styrene, etc.), and excellent water vapor barrier properties. Can be mentioned. In addition, since the amount of residual metal, monomer, etc. is small, the generation of unpleasant odor during modeling can be suppressed. In addition, it has a solidification rate suitable for the Fused Deposition Modeling method, surface treatment with a solvent is possible, flexibility can be imparted, it is safe for the human body, it has excellent optical characteristics, and electrical characteristics (low). Excellent dielectric properties, etc.).

Further, the cyclic olefin resin has an advantage that smoothing treatment, that is, polishing or surface treatment with a solvent is easy. In the case of the Fused Deposition Modeling method, layered streaks are more or less generated as the modeling material is laminated. In order to smooth the surface, polishing is performed as a post-treatment, or the surface is lightly dissolved with a solvent. In the case of cyclic polyolefin, the elastic modulus is generally high and it is easy to polish. Further, since it partially dissolves and swells in a hydrocarbon solvent at room temperature, it can be smoothed by wiping the surface with the solvent or immersing it in the solvent for a short time (for example, less than 1 minute).
Furthermore, the molded product made of cyclic olefin resin is also excellent in paintability. It is also possible to paint the modeled product as it is, or it is possible to paint after the above-mentioned smoothing treatment. It is often painted to improve the design.

As described above, the modeling material of the present embodiment containing the cyclic olefin resin does not have an unpleasant odor and is easy to surface-treat with a solvent, unlike the modeling material using ABS resin or PLA resin. Furthermore, since there are few residual metals and monomers, it is highly safe for the human body and can be applied to medical applications and food applications. It can also be used for dental materials and the like.
Further, since the cyclic olefin resin is excellent in transparency, it can also be used for modeling a modeled product that requires a skeleton or an optical member such as a lens.

However, when a cyclic olefin resin is used as a modeling material for a 3D printer, it may be difficult for the molten resin to follow the movement of the printer head due to the high viscosity of the molten resin, and it may be difficult to increase the modeling speed. That is, if the viscosity of the molten resin is too high, it is considered that if the molding speed is increased, the resin is pulled by the printer head that moves while discharging the molten resin, the modeling is disturbed, and it becomes difficult for the molten resin to follow the movement of the printer head. ..
According to the modeling material of the present embodiment, which comprises at least one selected from the group consisting of terpene resin and petroleum resin together with the cyclic olefin resin, it is possible to improve the followability of the molten resin and improve the modeling speed. It will be possible.

The components of the modeling material of the present embodiment will be described in detail below.

[Cyclic olefin resin]
The modeling material of this embodiment contains a cyclic olefin resin. The modeling material of the present embodiment may contain only one type of cyclic olefin resin, or may contain two or more types in combination.
The cyclic olefin resin is not particularly limited as long as it is a polyolefin resin containing a cyclic olefin component in the main chain. Examples of the cyclic olefin resin include a copolymer of an α-olefin and a cyclic olefin, a cyclic olefin ring-opening polymer, and a hydrogenated product of a cyclic olefin ring-opening polymer.
Further, the cyclic olefin resin is preferably amorphous in order to ensure transparency. Here, "amorphous" refers to a state in which no crystal melting peak is observed in the DSC measurement according to the transfer heat measurement method of JIS K 7121 plastic.

Further, examples of the cyclic olefin resin include those obtained by grafting and / or copolymerizing an unsaturated compound having a polar group.

Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, a hydroxyl group and the like, and examples of the unsaturated compound having a polar group include (meth) acrylic acid and malein. Acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (1-10 carbon atoms) ester, alkyl maleate (1-10 carbon atoms) ester, (meth) acrylamide, (meth) ) -2-Hydroxyethyl acrylate and the like can be mentioned.

As the cyclic olefin resin, a commercially available resin can also be used. Examples of commercially available cyclic olefin resins include TOPAS (registered trademark) (TOPAS Advanced Polymers) and Appel (registered trademark) (Mitsui Chemicals). Further, as a commercially available cyclic olefin polymer produced by ring-opening polymerization with a metathesis catalyst using a cyclic olefin component as a starting material and hydrogenating, for example, Zeonex (registered trademark) (manufactured by Japan Zeon Co., Ltd.) , Zeonoa (registered trademark) (manufactured by Nippon Zeon Co., Ltd.), Arton (registered trademark) (manufactured by JSR Corporation), and the like.

The α-olefin of the cyclic olefin resin is not particularly limited, but an α-olefin having 2 to 20 carbon atoms is preferable. For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene. , 4-Methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Further, these α-olefin components may be used alone or in combination of two or more. Of these, ethylene alone is most preferred.

Suitable cyclic olefin components in the cyclic olefin resin include, for example, cyclic olefins represented by the following general formula (A).

（式中、Ｒ^１〜Ｒ^１２は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、
Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、
Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。
また、ｎは、０又は正の整数を示し、ｎが２以上の場合には、Ｒ^５〜Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。）

(In the formula, R ^{1 to} R ¹² may be independently the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
R ⁹ and R ¹⁰ and R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group.
R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other.
Further, n indicates 0 or a positive integer, and when n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit. )

^{R 1 to} R ¹² in the general formula (A) may be independently the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Specific examples of R ^{1 to} R ⁸ include hydrogen atoms; halogen atoms such as fluorine, chlorine and bromine; lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group. May be different from each other, may be partially different, or may be all the same.

Specific examples of R ^{9 to} R ¹² include hydrogen atom; halogen atom such as fluorine, chlorine and bromine; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group and stearyl. Alkyl group such as group; Cycloalkyl group such as cyclohexyl group; Substituent or unsubstituted aromatic hydrocarbon group such as phenyl group, trill group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group; benzyl group, phenethyl Examples thereof include a group and an aralkyl group in which an aryl group is substituted for an alkyl group, and these may be different, partially different, or all may be the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are integrated to form a divalent hydrocarbon group include, for example, an alkylidene group such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the formed ring may be a monocyclic ring, a polycyclic ring, or a polycyclic ring having a crosslink. , It may be a ring having a double bond, or it may be a ring composed of a combination of these rings. Further, these rings may have a substituent such as a methyl group.

Specific examples of the cyclic olefin component represented by the general formula (A) include bicyclo [2.2.1] hepta-2-ene (common name: norbornene) and 5-methyl-bicyclo [2.2.1] hepta. -2-ene, 5,5-dimethyl-bicyclo [2.2.1] hepta-2-ene, 5-ethyl-bicyclo [2.2.1] hepta-2-ene, 5-butyl-bicyclo [2] .2.1] Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hepta-2-ene, 5-hexyl-bicyclo [2.2.1] hepta-2-ene, 5-octyl -Bicyclo [2.2.1] hepta-2-ene, 5-octadecyl-bicyclo [2.2.1] hepta-2-ene, 5-methylidene-bicyclo [2.2.1] hepta-2-ene , 5-Vinyl-bicyclo [2.2.1] hepta-2-ene, 5-propenyl-bicyclo [2.2.1] hepta-2-ene and other bicyclic cyclic olefins;

Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] deca-3-ene; tricyclo [ 4.4.0.1 ^2,5 ] Undeca-3,7-diene or tricyclo [4.4.0.1 ^2,5 ] Undeca-3,8-diene or a partial hydrogenation of these (or cyclopentadiene) Tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hepta-2-ene, 5-cyclohexyl-bicyclo 3 such as [2.2.1] hepta-2-ene, 5-cyclohexenylbicyclo [2.2.1] hepta-2-ene, 5-phenyl-bicyclo [2.2.1] hepta-2-ene. Cyclic olefin of the ring;

Tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] Dodeca-3-ene, 8-vinyltetracyclo [4,4.0.1, ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . ^17,10 ] 4-ring cyclic olefins such as dodeca-3-ene;

8-Cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] Dodeca-3-ene; Tetracyclo [7.4.1 ^3,6 . 0 ^{1,9 1} . 0 ^2,7 ] Tetradeca-4,9,11,13-tetraene (also called 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1, ^4,7 . 0 ^{1,10 1} . 0 ^3,8 ] Pentadeca-5,10,12,14-tetraene (also called 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene); pentacyclo [6.6.1] .1 ^3,6 . 0 ^2,7 . ^09,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [7.4.0.0 ^2,7. 1 ^{3, 6} . 1 ^{10, 13} ] -4-pentadecene; heptacyclo [8.7.0.1 ^2,9 . 1 ^{4, 7} . 1 ^{11, 17} ． 0 ^3,8 . 0 ^12,16 ] -5-eikosen, heptacyclo [8.7.0.1 ^2,9 . 0 ^3,8 . 1 ^{4, 7} . 0 ^12,17 . 11 ^{13, l6} ] -14-eicosene; polycyclic cyclic olefins such as a tetramer of cyclopentadiene can be mentioned.

These cyclic olefin components may be used alone or in combination of two or more. Among these, it is preferable to use bicyclo [2.2.1] hepta-2-ene (common name: norbornene) alone.

The polymerization method of the α-olefin component having 2 to 20 carbon atoms and the cyclic olefin component represented by the general formula (A) and the hydrogenation method of the obtained polymer are not particularly limited and are known. It can be done according to the method. It may be a random copolymerization or a block copolymerization, but a random copolymerization is preferable.

Further, the polymerization catalyst used is not particularly limited, and can be obtained by a well-known method using a conventionally well-known catalyst such as a Ziegler-Natta-based catalyst, a metathesis-based catalyst, or a metallocene-based catalyst. The cyclic olefin and α-olefin addition copolymer or hydrogenated product thereof preferably used in the present invention is preferably produced using a metallocene-based catalyst.

Examples of the metathesis catalyst include molybdenum or tungsten-based metathesis catalysts known as a catalyst for ring-opening polymerization of cycloolefin (for example, described in JP-A-58-127728, JP-A-58-129013, etc.). Further, the polymer obtained by the metathesis catalyst uses an inorganic carrier-supported transition metal catalyst or the like, and 90% or more of the double bond of the main chain and 98% or more of the carbon-carbon double bond in the aromatic ring of the side chain are hydrogen. It is preferable to add it.
Cyclic olefin copolymers may be preferred because of the variety of glass transition temperatures and the ease of adjustment.

The glass transition temperature of the cyclic olefin resin (hereinafter, may be referred to as “Tg” or “glass transition point”) is preferably 180 ° C. or lower, more preferably 160 ° C. or lower, 130 ° C. More preferably, it is below ° C. The lower limit is not particularly specified, but usually the one having a temperature of 0 ° C. or higher is used. If the Tg is less than 0 ° C., the transparency may decrease.
On the other hand, a desired Tg cyclic olefin resin can be obtained by blending a plurality of cyclic olefin resins having different glass transition points. In this case, since there is an additivity between the amount of each cyclic olefin resin before blending and Tg, the Tg of the cyclic olefin resin after blending can be predicted, and it is desired based on such prediction. Tg cyclic olefin resin can be obtained.
For example, a cyclic olefin resin having a Tg of 33 ° C. and a cyclic olefin resin having a Tg of 78 ° C. can be blended to obtain Tg of 50 ° C.

[At least one selected from the group consisting of terpene resin and petroleum resin]
The modeling material of the present embodiment includes at least one selected from the group consisting of terpene resin and petroleum resin.

The terpene resin may be one in which only the terpene compound is used as a monomer, and a component derived from the terpene compound and a component derived from another compound such as an aromatic-modified terpene resin obtained by modifying the terpene resin with an aromatic monomer. It may be a resin containing and. Examples of the aromatic-modified terpene resin include a terpene phenol resin which is a copolymer containing a terpene compound-derived component and an aromatic compound-derived component other than phenol, and a terpene phenol resin which is a copolymer containing a terpene compound-derived component and a phenol-derived component. Be done.
The terpene compound is generally a compound having _{a polymer of isoprene (C 5} H ₈ ) as a basic skeleton, and depending on the number of isoprene units, monoterpenes (C ₁₀ H ₁₆ ), sesquiterpenes (C ₁₅ H ₂₄ ), It is classified into diterpenes (C ₂₀ H ₃₂ ) and the like.
Commercially available terpene resin products include, for example, the YS resin series manufactured by Yasuhara Chemical Co., Ltd. (YS resin PX1250, etc.), and commercially available terpene phenol resin products include, for example, the YS Polystar TH series manufactured by Yasuhara Chemical Co., Ltd. (YS Polystar TH130, etc.). Can be mentioned.

Petroleum resins, for example, be a C ₅ fraction may be aliphatic petroleum resin as a raw material, or aromatic petroleum resin a C ₉ fraction as a raw material. Further, for example, a C ₅ fraction a main material, dicyclopentadiene - can also be used aromatic copolymer type resin.

A resin containing a petroleum-based component and a component derived from a terpene compound (for example, an aromatic-modified terpene resin) can be included in both the terpene resin and the petroleum resin.
From the viewpoint of not impairing the transparency of the cyclic olefin resin, the terpene resin and the petroleum resin are preferably hydrogenated resins (hydrides), respectively.

The hydrogenated terpene resin is not particularly limited, and known ones can be used. Examples of the hydrogenated terpene resin include hydrogenated terpene resin obtained by hydrogenating terpene resin, aromatic modified terpene resin hydride obtained by hydrogenating aromatic modified terpene resin, and terpene phenol resin hydride obtained by hydrogenating terpene phenol resin. Can be mentioned.

Commercially available hydrogenated terpene resins include, for example, Clearon P series manufactured by Yasuhara Chemical Co., Ltd. (Clearon P115, etc.), and commercially available aromatic modified terpene resin hydrides include, for example, Clearron M series manufactured by Yasuhara Chemical Co., Ltd. (Clearon M115). , Etc.), Examples of commercially available terpene phenol resin hydrides include YS Polystar UH series (YS Polystar UH115, etc.) manufactured by Yasuhara Chemical Co., Ltd.

The hydrogenated petroleum resin is not particularly limited, and known hydrogenated petroleum resins can be used. Examples of the _{hydrogenated petroleum resin include C 5} -aromatic hydrogenated _{petroleum resin, hydrogenated C 9} hydrogenated petroleum resin, hydrogenated dicyclopentadiene petroleum resin, hydrogenated bearon inden resin and the like. From the viewpoint of not impairing the transparency of the cyclic olefin resin, a hydrogenated petroleum resin having higher transparency is preferable. Examples of highly transparent hydrogenated petroleum resins include Imarve (registered trademark) series (dicyclopentadiene-aromatic copolymer hydrogenated resin) (Imarb P-125, etc.) manufactured by Idemitsu Kosan Co., Ltd., Arakawa Chemical Industry Co., Ltd. Examples thereof include Archon (registered trademark) series (alicyclic saturated hydrocarbon resin) manufactured by Archon Co., Ltd. (Arcon P-115, Archon P-125, etc.).

The amount of at least one selected from the group consisting of terpene resin and petroleum resin is not particularly limited, but is preferably 5 to 45% by mass with respect to the modeling material. The amount of at least one selected from the group consisting of terpene resin and petroleum resin is preferably 5% by mass or more, more preferably 10% by mass or more, based on the molding material, from the viewpoint of the viscosity of the molten resin and the molding speed. , 15% by mass or more is more preferable, and 20% by mass or more is further preferable. Further, the amount of at least one selected from the group consisting of terpene resin and petroleum resin is preferably 45% by mass or less with respect to the modeling material from the viewpoint of reducing smoke generated from the terpene resin and petroleum resin during modeling. , 40% by mass or less is more preferable, and 35% by mass or less is further preferable.

[Other ingredients]
Other components such as a colorant, a filler, a stabilizer, an impact improver, a lubricant, an antistatic agent, and an ultraviolet absorber may be added to the modeling material of the present embodiment, depending on its use.
The addition of other components is optional. The modeling material may be composed of, for example, a cyclic olefin resin and at least one selected from the group consisting of a terpene resin and a petroleum resin.
Further, in addition to at least one selected from the group consisting of cyclic olefin resins, terpene resins and petroleum resins, various other polyolefins may be further added to the molding material, and such polyolefins may be used. For example, polyethylene, polypropylene and the like can be mentioned. In particular, straight-chain low-density polyethylene has excellent compatibility with cyclic olefin resins and can be blended in any ratio. When the toughness is insufficient only with the cyclic olefin resin, the toughness can be improved by blending the linear low density polyethylene.

In the modeling material of the present embodiment, the melt index value at 230 ° C. and a load of 2.16 kg is preferably 15 g / 10 min to 80 g / 10 min, more preferably 15 g / 10 min to 76 g / 10 min, and 15 g. It is more preferably / 10min to 70g / 10min. The melt index at 230 ° C. and a load of 2.16 kg is preferably 15 g / 10 min or more, and more preferably 20 g / 10 min or more, from the viewpoint of the viscosity of the molten resin and the molding speed. Further, the melt index at 230 ° C. and a load of 2.16 kg is preferably 80 g / 10 min or less, more preferably 76 g / 10 min or less, and 70 g / 10 min or less from the viewpoint of ease of filament production. Is even more preferable, 60 g / 10 min or less is further preferable, and 55 g / 10 min or less is further preferable.

The melt index is a value measured under the conditions of 230 ° C. and a load of 2.16 kg by a method according to JIS K7210.

In the heat-melt lamination method, it is required that the layer once formed is not deformed by the heat and pressure of the layer to be laminated next. From this viewpoint, the molding material of the present embodiment has a thermal deformation temperature of 0 ° C. or higher. It is preferable that the temperature is 30 ° C. or higher. The upper limit of the thermal deformation temperature is not particularly specified, but may be, for example, 200 ° C., more preferably 180 ° C. or lower.

In a fused deposition modeling 3D printer, a filamentous molding material is usually supplied in a form of being wound around a spool.
The modeling material of this embodiment is generally in the form of a filament. When the modeling material of the present embodiment is filamentous, the filament diameter is preferably, for example, 0.5 mm to 5.0 mm. The filament diameter can be appropriately selected depending on the model of the 3D printer. For example, in the model with the filament diameter set to 1.75 mm, the filament diameter is preferably 1.70 mm to 1.80 mm, for example, the model with the filament diameter set to 3.0 mm. The filament diameter is preferably 2.95 mm to 3.05 mm.

The method for forming the filament is not particularly limited, and examples thereof include the following methods. That is, a composition containing each of the above components including the cyclic olefin resin is melt-kneaded using an extruder or the like, melt-extruded from a die nozzle, and the extruded composition is taken up into a strand shape. This strand-shaped composition is cooled using a cooling medium such as water or air for spinning, and then, if necessary, heat-stretching, heat treatment, oil coating, or the like is performed, and the filament is wound up. It becomes a state.

The cross-sectional shape of the filament is not particularly limited, and examples thereof include a circle, an ellipse, a triangle, a quadrangle, a hexagon, and a star.

If the resin of the modeling material has high water absorption, the molten resin may foam and the filament may break. Since the modeling material of the present embodiment contains a cyclic olefin resin having low water absorption, it is possible to reduce the occurrence of such problems.

2. Method for manufacturing a three-dimensional object The method for manufacturing a three-dimensional object according to the embodiment of the present invention includes modeling a three-dimensional object with a 3D printer by a fused deposition modeling method using the modeling material of the above-described embodiment. be.
When modeling with a hot melt lamination type 3D printer using the modeling material of the above-described embodiment, the nozzle temperature is preferably 120 to 250 ° C. Further, since the modeling material of the above-described embodiment has little thermal deformation, it may not be necessary to heat the modeling table.
The stacking pitch is usually 0.05 to 0.5 mm. The stacking pitch can be determined by adjusting the nozzle diameter and extrusion conditions.

Embodiments of the present invention include: However, the present invention is not limited to the following embodiments.
<1> A modeling material used for a fused deposition modeling 3D printer, which comprises a cyclic olefin resin and at least one selected from the group consisting of a terpene resin and a petroleum resin.
<2> The modeling material according to <1>, wherein the melt index value at 230 ° C. and a load of 2.16 kg is 15 to 80 g / 10 min.
<3> The modeling material according to <1> or <2>, which is filamentous.
<4> At least one selected from the group consisting of the terpene resin and the petroleum resin includes at least one selected from the group consisting of the hydrogenated terpene resin and the hydrogenated petroleum resin, <1> to <3>. The modeling material according to any one of the above items.
<5> Any one of <1> to <4>, wherein the content of at least one selected from the group consisting of the terpene resin and the petroleum resin is 5 to 45% by mass with respect to the modeling material. The modeling material described in.
<6> A method for manufacturing a three-dimensional object, which comprises modeling a three-dimensional object with a fused deposition modeling 3D printer using the modeling material according to any one of <1> to <5>.

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Comparative Example 1]
<Making modeling materials>
Cyclic olefin resin TOPAS (registered trademark) 8007F-04 (TOPAS Advanced Polymers, Tg: 78 ° C.) was used as an extruder at TEX30C manufactured by Japan Steel Works, Ltd. at a cylinder temperature of 200 ° C. and a screw rotation speed of 200 rpm. Melt extrusion was performed. After extrusion, the obtained strands were cooled in a water tank and then taken up at a constant speed using a mesh conveyor to prepare a filament-shaped modeling material having a diameter of 1.7 mm.

<Fused Deposition Modeling, Evaluation of Modeling Speed, and Evaluation of Smoke During Modeling>
The produced filament-shaped modeling material is set in a 3D printer (ATOM manufactured by Genkei), and modeling is performed at the modeling speed (10 mm / sec or 20 mm / sec) shown in Table 1 under the following conditions to obtain a height. A cup-shaped modeled product having a diameter of 26 mm, a bottom diameter of 14 mm, an opening diameter of 21 mm, and a wall surface thickness of 1.3 mm was produced.
The produced modeled products were evaluated for the presence or absence of modeling errors. The 3D printer head repeats a circular motion to pile up the molten filaments, but the molten filaments cannot follow the movement of the printer head and are shaped as "strings" instead of "arcs". As a result, B was designated as having such a modeling error. No molding mistakes If the molding speed is higher, it indicates that the molding speed is improved.
In addition, the presence or absence of smoke during modeling was evaluated. The case where smoke was not observed from the filament melted during molding was designated as A, and the case where smoke was observed was designated as B.
The results are shown in Table 1.
Modeling conditions:
Nozzle temperature (modeling temperature) 230 ° C
Discharge diameter 0.4 mm
Lamination pitch 0.2 mm

<Melt index at 230 ° C and load 2.16 kg>
The melt index of the produced modeling material was measured using a melt indexer manufactured by Toyo Seiki Co., Ltd. under the conditions of 230 ° C. and a load of 2.16 kg by a method conforming to JIS K7210. The results are shown in Table 1.

[Examples 1 to 4]
In the production of modeling materials, instead of the cyclic olefin resin TOPAS (registered trademark) 8007F-04, the cyclic olefin resin TOPAS (registered trademark) 8007F-04 and the aromatic-modified terpene resin hydride Clearon M115 (manufactured by Yasuhara Chemical Co., Ltd.) In the same manner as in Comparative Example 1, the production of the modeling material, the modeling by the heat-melt lamination method, the evaluation of the modeling speed, and the evaluation of the presence or absence of smoke during modeling were performed in the same manner as in Comparative Example 1 except that the contents shown in Table 1 were used. , And the melt index were measured. The results are shown in Table 1.
In the table, "8007F-04" indicates "TOPAS (registered trademark) 8007F-04".

[Example 5]
In the production of modeling materials, instead of the cyclic olefin resin TOPAS (registered trademark) 8007F-04, the cyclic olefin resin TOPAS (registered trademark) 8007F-04 and the hydrogenated terpene resin Clearon P115 (manufactured by Yasuhara Chemical Co., Ltd.) are shown in Table 1. In the same manner as in Comparative Example 1, except that the content was used so as to be as described in the above, preparation of a modeling material, modeling by a heat-melt lamination method, evaluation of a modeling speed, evaluation of the presence or absence of smoke during modeling, and melting. The index was measured. The results are shown in Table 1.

[Example 6]
In the production of modeling materials, instead of the cyclic olefin resin TOPAS (registered trademark) 8007F-04, the cyclic olefin resin TOPAS (registered trademark) 8007F-04 and the terpene phenol resin YS Polystar TH130 (manufactured by Yasuhara Chemical Co., Ltd.) are shown in Table 1. In the same manner as in Comparative Example 1, except that the content was used so as to be as described in the above, preparation of a modeling material, modeling by a hot melt lamination method, evaluation of a modeling speed, evaluation of the presence or absence of smoke during modeling, and melting. The index was measured. The results are shown in Table 1.

[Example 7]
In the production of modeling materials, instead of the cyclic olefin resin TOPAS (registered trademark) 8007F-04, the cyclic olefin resin TOPAS (registered trademark) 8007F-04 and the terpene phenol resin hydride YS Polystar UH115 (manufactured by Yasuhara Chemical Co., Ltd.) are used. Similar to Comparative Example 1, except that the contents were used so as to be as shown in Table 1, preparation of a modeling material, modeling by a heat-melt lamination method, evaluation of modeling speed, evaluation of the presence or absence of smoke during modeling, And the melt index was measured. The results are shown in Table 1.

[Example 8]
In the production of molding materials, instead of the cyclic olefin resin TOPAS (registered trademark) 8007F-04, the cyclic olefin resin TOPAS (registered trademark) 8007F-04 and the alicyclic saturated hydrocarbon resin (hydrogenated petroleum resin) Archon P In the same manner as in Comparative Example 1, except that −115 (manufactured by Arakawa Chemical Industry Co., Ltd.) was used so as to have the content shown in Table 1, the production of the modeling material, the modeling by the thermal melt lamination method, and the modeling speed Evaluation, evaluation of the presence or absence of smoke during modeling, and measurement of the melt index were performed. The results are shown in Table 1.

[Example 9]
In the production of molding materials, instead of the cyclic olefin resin TOPAS (registered trademark) 8007F-04, the cyclic olefin resin TOPAS (registered trademark) 8007F-04 and the dicyclopentadiene-aromatic copolymer hydrogenated petroleum resin Imarb P Preparation of molding material, molding by thermal melt lamination method, evaluation of molding speed in the same manner as in Comparative Example 1 except that −125 (manufactured by Idemitsu Kosan Co., Ltd.) was used so as to have the content shown in Table 1. , The presence or absence of smoke during modeling was evaluated, and the melt index was measured. The results are shown in Table 1.

[Comparative Example 2]
Comparative Example 1 and Comparative Example 1 except that the cyclic olefin resin Apel 8008T (manufactured by Mitsui Chemicals, Inc., Tg: 70 ° C.) was used instead of the cyclic olefin resin TOPAS (registered trademark) 8007F-04 in the production of the modeling material. In the same manner, preparation of a modeling material, modeling by the Fused Deposition Modeling method, evaluation of the modeling speed, evaluation of the presence or absence of smoke during modeling, and measurement of the melt index were performed. The results are shown in Table 1.
In the table, "8008T" indicates "Apel 8008T".

[Example 10]
Comparison except that cyclic olefin resin Apel 8008T and hydrogenated aromatic modified terpene resin Clearon M115 were used instead of cyclic olefin resin Apel 8008T in the preparation of the modeling material so as to have the contents shown in Table 1. In the same manner as in Example 2, preparation of a molding material, molding by a heat-melt lamination method, evaluation of a molding speed, evaluation of the presence or absence of smoke during molding, and measurement of a melt index were performed. The results are shown in Table 1.

[Comparative Example 3]
In the production of the modeling material, the cyclic olefin resin TOPAS (registered trademark) 8007S-04 (manufactured by TOPAS Advanced Polymers, Tg: 78 ° C.) was used instead of the cyclic olefin resin TOPAS (registered trademark) 8007F-04. Except for the above, in the same manner as in Comparative Example 1, production of a modeling material, modeling by the Fused Deposition Modeling method, evaluation of the modeling speed, evaluation of the presence or absence of smoke during modeling, and measurement of the melt index were performed. The results are shown in Table 2.
In the table, "8007S-04" indicates "TOPAS (registered trademark) 8007S-04".

[Examples 11 to 14]
In the production of modeling materials, instead of the cyclic olefin resin TOPAS (registered trademark) 8007S-04, the cyclic olefin resin TOPAS (registered trademark) 8007S-04 and the alicyclic saturated hydrocarbon resin (hydrogenated petroleum resin) Archon P In the same manner as in Comparative Example 3, except that −125 (manufactured by Arakawa Chemical Industry Co., Ltd.) was used so as to have the content shown in Table 2, the production of the modeling material, the modeling by the thermal melt lamination method, and the modeling speed Evaluation, evaluation of the presence or absence of smoke during modeling, and measurement of the melt index were performed. The results are shown in Table 2.

From Tables 1 and 2, in Examples 1 to 14, no molding error was observed at a molding speed of 10 mm / sec. On the other hand, in all of Comparative Examples 1 to 3, a molding error occurred at a molding speed of 10 mm / sec, and in Examples 1 to 14, the molding speed was improved as compared with Comparative Examples 1 to 3. You can see that.

The disclosure of Japanese Patent Application No. 2016-120535 filed on June 17, 2016 is incorporated herein by reference in its entirety.
It should be noted that in addition to those already described, various modifications and modifications may be made to the above embodiments without departing from the novel and advantageous features of the present invention. Therefore, all such modifications and changes are intended to be included in the appended claims.

Claims (9)

A molding material used for a fused deposition modeling 3D printer, which contains a cyclic olefin resin and a terpene resin (excluding terpene phenol resin) , and has a melt index value at 230 ° C. and a load of 2.16 kg. A modeling material that weighs 15 g / 10 min or more. The modeling material according to claim 1, wherein the terpene resin contains a hydrogenated terpene resin. The modeling material according to claim 1 or 2, wherein the content of the terpene resin is 5 to 45% by mass with respect to the modeling material. A molding material used in a fused deposition modeling 3D printer, which comprises a cyclic olefin resin and at least one selected from the group consisting of a terpene resin (excluding a terpene phenol resin) and a petroleum resin.
The cyclic olefin resin is at least one selected from the group consisting of a copolymer of an α-olefin and a cyclic olefin, a cyclic olefin ring-opening polymer, and a hydrogenated product of the cyclic olefin ring-opening polymer.
The petroleum resin is at least one selected from the group consisting of aromatic petroleum resins and dicyclopentadiene-aromatic copolymer petroleum resins.
A modeling material having a melt index value of 15 g / 10 min or more at 230 ° C. and a load of 2.16 kg. The modeling material according to claim 4, wherein at least one selected from the group consisting of the terpene resin and the petroleum resin contains at least one selected from the group consisting of the hydrogenated terpene resin and the hydrogenated petroleum resin. The modeling material according to claim 4 or 5, wherein the content of at least one selected from the group consisting of the terpene resin and the petroleum resin is 5 to 45% by mass with respect to the modeling material. The modeling material according to any one of claims 1 to 6, wherein the melt index value at 230 ° C. and a load of 2.16 kg is 15 to 80 g / 10 min. The modeling material according to any one of claims 1 to 7, which is filamentous. A method for manufacturing a three-dimensional object, which comprises modeling a three-dimensional object with a fused deposition modeling 3D printer using the modeling material according to any one of claims 1 to 8.