WO2023095393A1 - Composition de résine chargée d'une poudre de substance inorganique et produit moulé - Google Patents

Composition de résine chargée d'une poudre de substance inorganique et produit moulé Download PDF

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Publication number
WO2023095393A1
WO2023095393A1 PCT/JP2022/030749 JP2022030749W WO2023095393A1 WO 2023095393 A1 WO2023095393 A1 WO 2023095393A1 JP 2022030749 W JP2022030749 W JP 2022030749W WO 2023095393 A1 WO2023095393 A1 WO 2023095393A1
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resin
mass
resin composition
filled
inorganic substance
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PCT/JP2022/030749
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Japanese (ja)
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祐介 服部
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株式会社Tbm
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to inorganic substance powder-filled resin compositions and molded articles. Specifically, the present invention provides an inorganic substance powder-filled resin composition suitable as a filament material for 3D printers, which exhibits good shape retention, excellent modeling accuracy, and high impact resistance, and a resin composition using the same. It relates to shaped articles, including 3D filament materials.
  • the Fused Deposition Modeling (FDM) method is often used because of its simplicity.
  • a raw material is generally inserted into an extrusion head as a filament made of a thermoplastic resin, and while being heated and melted, is continuously extruded from a nozzle portion provided in the extrusion head onto an XY plane substrate in a chamber, A step of depositing and fusing the extruded resin on an already deposited resin laminate and then cooling and solidifying it is taken.
  • thermoplastic resins such as ABS resins (acrylonitrile-butadiene-styrene resins), polylactic acid (PLA), and polyolefin resins are generally suitably used from the viewpoint of workability and fluidity.
  • Patent Document 1 discloses an FDM filament composed of a polypropylene resin having a specific melt mass flow rate, an olefin copolymer rubber, and a softening agent.
  • Patent Document 2 describes FDM filaments containing a specific propylene copolymer.
  • Patent Document 3 discloses FDM filaments containing polypropylene branched with a specific peroxide.
  • Blending a filler such as an inorganic powder into the FDM filament resin composition is also under consideration.
  • Patent Document 4 discloses an FDM filament containing specific polypropylene and calcium carbonate at a mass ratio of 20:80 to 50:50. This filament has the advantages of high reproducibility in 3D printer modeling and easy post-processing.
  • Patent Document 5 discloses FDM modeling filaments containing functional nanofillers such as carbon nanotubes and nanoclays.
  • filaments based on polyolefin resin cannot be ignored due to heat shrinkage during molding, and filaments based on soft polyolefin resin in particular have the disadvantage of poor shape retention.
  • Heat shrinkage can be suppressed by blending a filler, and shape retention can be improved by blending polyethylene or polypropylene (homopolymer).
  • shape retention can be improved by blending polyethylene or polypropylene (homopolymer).
  • the obtained filaments tend to be hard and brittle.
  • the functional nanofiller as described in Patent Document 5 has a strong interaction with the resin component, the filament becomes hard and difficult to process unless the blending amount is suppressed to about several mass %. put away.
  • the amount of filler compounded is small, the problems of heat shrinkage and warpage during molding cannot be solved.
  • the present invention has been made in view of the above circumstances, and exhibits good shape retention by suppressing heat shrinkage and warping during molding, is flexible and easy to post-process, and has excellent molding accuracy and high molding accuracy.
  • An object of the present invention is to provide an inorganic powder-filled resin composition having impact resistance and suitable as a filament material for FDM, and a molded article such as a 3D filament material using the same.
  • the inventors of the present invention have made intensive studies to solve the above problems.
  • the inventors have found that it is possible to obtain an inorganic powder-filled resin composition suitable as a filament material for FDM, which is suppressed, is flexible, and has excellent impact resistance, and arrived at the present invention.
  • the present invention provides an inorganic powder-filled resin composition containing a thermoplastic resin and an inorganic powder in a mass ratio of 50:50 to 10:90,
  • the thermoplastic resin contains a first resin and a second resin,
  • the first resin is a propylene- ⁇ -olefin copolymer,
  • the second resin is a polyolefin resin different from the first resin, and the content of the first resin is 80 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
  • An inorganic substance powder-filled resin composition characterized by:
  • the present invention also provides an inorganic substance powder-filled resin composition for fused deposition deposition method 3D printer filaments containing a thermoplastic resin and an inorganic substance powder at a mass ratio of 50:50 to 10:90,
  • the thermoplastic resin contains a first resin and a second resin,
  • the first resin is a propylene- ⁇ -olefin copolymer,
  • the second resin is a polyolefin resin different from the first resin, and the content of the first resin is 80 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
  • An inorganic substance powder-filled resin composition for fused deposition deposition method 3D printer filaments characterized by:
  • the second resin is a propylene homopolymer and/or block polypropylene.
  • the first resin is an ethylene-propylene copolymer having propylene repeating units and a random ethylene distribution
  • the propylene-derived structural units are An inorganic powder-filled resin composition containing 80% by mass or more and 20% by mass or less of structural units derived from ethylene is indicated.
  • an inorganic substance powder-filled resin composition is shown in which the inorganic substance powder is calcium carbonate.
  • the inorganic powder-filled resin composition is indicated in which the calcium carbonate is surface-treated heavy calcium carbonate.
  • the inorganic substance has an average particle size of 0.7 ⁇ m or more and 6.0 ⁇ m or less by an air permeation method according to JIS M-8511 of the calcium carbonate. A powder-filled resin composition is shown.
  • the present invention for solving the above problems is also a molded article made of the above inorganic substance powder-filled resin composition.
  • the molded article is an extruded article.
  • the molded article is a fused layering method 3D printer filament.
  • an inorganic substance powder filling that exhibits good shape retention by suppressing heat shrinkage and warpage during molding, is flexible, facilitates post-processing, excels in molding accuracy, and has high impact resistance.
  • Resin compositions and inorganic powder-filled resin compositions for fused deposition deposition 3D printer filaments are provided.
  • the inorganic powder-filled resin composition of the present invention is also useful as a material other than filaments for FDM, and can be molded into various molded articles including various extruded articles.
  • the inorganic powder-filled resin composition of the present invention and the inorganic powder-filled resin composition for hot melt deposition method 3D printer filament of the present invention contain a thermoplastic resin and an inorganic powder at a mass ratio of 50:50 to 10:50:50. 90% inorganic powder-filled resin composition, wherein the thermoplastic resin comprises a first resin and a second resin, the first resin being a propylene- ⁇ -olefin copolymer and the second resin is a polyolefin resin different from the first resin, and the content of the first resin is 80 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. It is characterized by
  • the inorganic powder-filled resin composition of the present invention contains two types of polyolefin resins with different properties as thermoplastic resins in a well-balanced manner, so it exhibits excellent physical properties in terms of both shape retention and flexibility. Therefore, post-processing is easy, and the molded product exhibits good impact resistance. In addition, since a large amount of inorganic substance powder is filled, heat shrinkage and warpage during modeling are suppressed. As a result, an inorganic powder-filled resin composition that exhibits extremely good shape retention, is easy to post-process, and has excellent impact resistance is obtained. Therefore, the inorganic powder-filled resin composition of the present invention is suitable for applications such as filament materials for FDM.
  • each component constituting the inorganic powder-filled resin composition (hereinafter sometimes abbreviated as "resin composition") according to the present invention will be described in detail.
  • the inorganic powder-filled resin composition according to the present invention contains at least two types of polyolefin resins as thermoplastic resins.
  • the first resin is a propylene- ⁇ -olefin copolymer
  • the second resin is a polyolefin resin having a structure different from that of the first resin.
  • the propylene- ⁇ -olefin copolymer contained as the first resin
  • copolymer Various copolymers are commercially available.
  • the copolymer that can be used in the present invention is not particularly limited, and various copolymers can be used depending on the application, function, etc. of the resin composition. It is also possible to use two or more copolymers together.
  • Monomers for copolymerization with propylene are also not particularly limited, and may be, for example, one or more monomer components selected from ethylene and ⁇ -olefins having 4 to 10 carbon atoms.
  • Examples include ethylene, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1-butene, 1-heptene, 3-methyl-1-hexene, 1 - including but not limited to octene;
  • copolymers with ethylene, 1-butene, isobutylene, 1-hexene, and/or 1-octene, especially ethylene are preferred.
  • the form of copolymerization is also not limited, and various forms of copolymers such as random copolymers, block copolymers, alternating copolymers, and graft copolymers can be used.
  • a copolymer having a random distribution of propylene repeating units and a random ⁇ -olefin component, for example, a random ethylene distribution is preferred because it maintains workability and flexibility even when a large amount of inorganic substance powder is filled.
  • the first resin is an ethylene-propylene copolymer having isotactic propylene repeating units and a random ethylene distribution.
  • isotactic propylene repeat units can form crystalline regions, which facilitates toughness and dimensional stability.
  • the random ethylene distribution imparts flexibility, the resin composition has excellent impact resistance.
  • the propylene- ⁇ -olefin copolymers that may be used in the present invention may also have a triad tacticity of 3 propylene units. Triad tacticity can be measured, for example, by 13 C-nuclear magnetic resonance (NMR) and can typically have values of the order of 50-99%, especially 75-99%.
  • the copolymerization ratio is also not particularly limited, but a copolymer containing preferably 5% by mass or more, more preferably 7% by mass or more, and particularly preferably 8% by mass or more, is an ⁇ -olefin-derived structural unit that is a copolymerization monomer. Also, a copolymer containing the same constituent unit preferably at 35% by mass or less, more preferably at most 25% by mass, still more preferably at most 20% by mass, particularly preferably at most 18% by mass, is used.
  • the propylene- ⁇ -olefin copolymer having such a copolymerization ratio is highly flexible and has excellent compatibility with other polyolefin resins as the second resin described later. When incorporated into a composition, it can exhibit particularly excellent flexibility and workability.
  • the propylene- ⁇ -olefin copolymer that can be used in the present invention may also contain a structural unit derived from a third component such as a diene or a carboxylic acid (ester)-modified olefin.
  • the diene component includes 1,4-hexadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, dicyclopentadiene (DCPD), ethylidenenorbornene (ENB ), norbornadiene, 5-vinyl-2-norbornene, etc.; carboxylic acid (ester)-modified olefins include carboxyl group-containing olefins, carboxylic acid ester group-containing olefins, such as maleic anhydride-modified olefins, (meth)acrylic acid Examples include, but are not limited to, methyl and the like, respectively.
  • a copolymer containing, for example, 0.1 to 10% by mass, particularly 0.5 to 8% by mass, especially 1 to 5% by mass, of structural units derived from these third components is a propylene- ⁇ - It may exhibit melting behavior and compatibility different from those of olefin copolymers, and it is also possible to control the physical properties and workability of the inorganic powder-filled resin composition of the present invention by blending them. Since the diene-derived structural unit can also serve as a cross-linking site, the propylene- ⁇ -olefin copolymer is partially cross-linked by mixing it with other components together with a cross-linking agent such as a peroxide to modify processability. You can also Further, by using a propylene- ⁇ -olefin copolymer having functional groups such as carboxylic acid groups, miscibility with inorganic substance powders may be enhanced, and physical properties and moldability may be improved.
  • the propylene- ⁇ -olefin copolymer as described above is generally flexible, and has, for example, a Shore A hardness of 10 to 90, typically 20 to 80, based on JIS K6253-3:2012.
  • the inorganic powder-filled resin composition of the present invention is excellent in flexibility and impact resistance because these copolymers are blended.
  • Propylene- ⁇ -olefin copolymers have a wide variety of properties, for example, a mass average molecular weight of 20,000 to 5,000,000, typically 50,000 to 1,000,000, particularly 70,000 to 400.
  • melt flow rate MFR at 2.16 kg, 230° C. according to ASTM D1238, of 0.1-90 g/10 min, typically 0.5-30 g/10 min; about 10 minutes; the melting temperature can range from 40 to 180° C., typically from 80 to 160° C., particularly from 100 to 140° C., but is not limited thereto; Propylene- ⁇ -olefin copolymers with similar properties can also be used.
  • the content of the propylene- ⁇ -olefin copolymer, which is the first resin is 80 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. is. If the content of the propylene- ⁇ -olefin copolymer is 80% by mass or more of the total thermoplastic resin, the workability and flexibility of the resin composition are hardly impaired even if the inorganic powder is highly filled. In addition, when the content of the copolymer is 95 parts by mass or less, a resin composition (or filament) is provided which is excellent in shape retention and molding accuracy, in which shrinkage during molding is suppressed.
  • the content of the first resin with respect to 100 parts by mass of the thermoplastic resin is preferably 85 parts by mass or more and 93 parts by mass or less, more preferably 87 parts by mass or more and 92 parts by mass or less.
  • the second resin in the inorganic powder-filled resin composition of the present invention may be any polyolefin resin different from the first resin, and various resins may be used depending on the purpose. can do.
  • the polyolefin-based resin is a polyolefin-based resin mainly composed of olefin component units, and specifically includes polypropylene-based resin, polyethylene-based resin, polymethyl-1-pentene, cyclic olefin polymer, Examples include olefin copolymers and mixtures of two or more thereof.
  • the above-mentioned "mainly composed” means that the olefin component unit is contained in the polyolefin resin in an amount of 50% by mass or more, and the content is preferably 75% by mass or more, more preferably 85% by mass. % or more, more preferably 90 mass % or more.
  • homopolymers (homopolymers) of polyolefins are preferred.
  • the method for producing the polyolefin resin used in the present invention is not particularly limited, and can be obtained by any method using a Ziegler-Natta catalyst, a metallocene catalyst, or a radical initiator such as oxygen or peroxide. It may be something else.
  • a resin that is preferable as the second resin in the present invention is a polyethylene-based resin and/or a polypropylene-based resin.
  • polyethylene-based resins and polypropylene-based resins include resins containing 50% by mass or more of ethylene units or propylene component units.
  • a copolymer with tetrafluoroethylene, vinyl acetate, (meth)acrylic acid (ester), or the like may also be used.
  • polyethylene-based resins include high-density polyethylene (HDPE), low-density polyethylene (LDPE), medium-density polyethylene, linear low-density polyethylene (LLDPE), ethylene-vinyl acetate copolymer, ethylene-(meth) Acrylic acid (ester) copolymers and the like can also be used.
  • Copolymers of propylene with minor amounts of other monomers may also be used.
  • the second resin in the present invention is more preferably propylene homopolymer and/or block polypropylene.
  • These polypropylene-based resins have an excellent balance between mechanical strength and heat resistance, and provide excellent shape retention when blended in a resin composition filled with an inorganic powder.
  • Propylene homopolymer is a polymer obtained by polymerizing substantially only propylene, and is excellent in rigidity and heat resistance.
  • PP polypropylene homopolymer
  • Various products are commercially available, such as Wintec (registered trademark) and Novatec (registered trademark) of Japan Polypropylene Corporation, Noblen (registered trademark) of Sumitomo Chemical Co., Ltd., and Prime Polypro (registered trademark) of Prime Polymer Co., Ltd. ), Toray Industries, Inc.
  • the present invention is not limited to these, and any Such PP may be included.
  • a plurality of types of PP can also be used together.
  • Propylene homopolymers are classified into isotactic PP, syndiotactic PP, atactic PP, hemiisotactic PP, etc., depending on the difference in stereoregularity.
  • the resin composition of the present invention may contain any of these, and a plurality of these may be used in combination.
  • the homopolymer may contain trace components produced as a by-product during polymerization, or may have a branched structure.
  • a structure as if an ⁇ -olefin such as hexene is copolymerized may be contained in an amount of 5% by mass or less, particularly 1% by mass or less. It is broadly included as a propylene homopolymer (propylene homopolymer).
  • the molecular weight of the propylene homopolymer there is no particular limitation on the molecular weight of the propylene homopolymer.
  • PP having a weight average molecular weight of about 50,000 to 500,000, particularly about 100,000 to 400,000.
  • a compound having a mass average molecular weight of approximately 50,000 or more and less than 200,000 and a compound having a mass average molecular weight of approximately 200,000 or more and 500,000 or less can be used together.
  • Block polypropylene is a polymer having a sea-island structure in which polyethylene or the like is dispersed in PP, and is a kind of propylene block copolymer in a broad sense.
  • it is a polymer containing about 10 to 50% by mass of an island phase of a polyethylene component and/or an ethylene-propylene copolymer component in a PP sea phase, and is also called a heterophasic copolymer.
  • homopolypropylene chains and polyethylene chains or ethylene-propylene copolymer chains are not necessarily chemically bonded.
  • the propylene- ⁇ -olefin copolymer In this respect, it is clearly distinguished from the first resin, the propylene- ⁇ -olefin copolymer.
  • the polyethylene island phase In general block polypropylene, the polyethylene island phase is dispersed in the polypropylene sea phase while being covered with the ethylene-propylene copolymer. The mass ratio of (copolymer) to the second resin is hardly changed.
  • the above heterophasic copolymer can be produced, for example, by first polymerizing a propylene homopolymer and then copolymerizing ethylene or the like.
  • the sea-island structure can be controlled by adjusting the ratio of the ethylene component, the number of chains, and the molecular weight of the PP.
  • Various products are commercially available and any type of block polypropylene can be used in the present invention.
  • Block polypropylene is generally excellent in flexibility and impact resistance, and therefore, when used as the second resin in the present invention, it is possible to obtain a more flexible inorganic powder-filled resin composition.
  • thermoplastic resin includes the above-mentioned propylene- ⁇ -olefin copolymer and other polyolefin resins, and may further include resin components other than these.
  • Thermoplastic resins such as poly (meth) acrylic acid (ester), polyvinyl acetate, polyacrylonitrile, polystyrene, ABS resin, polycarbonate, polyamide, polyvinyl alcohol, petroleum hydrocarbon resin, coumarone-indene resin; Elastomers such as butadiene copolymers, styrene-isoprene copolymers, styrene-butadiene-ethylene copolymers, styrene-isoprene-ethylene copolymers, acrylonitrile-butadiene copolymers, fluorine-based elastomers, etc., may be mentioned. Not limited.
  • the thermoplastic resin in the inorganic powder-filled resin composition of the present invention is preferably 90% by mass or more, more preferably 97% by mass or more, and particularly preferably substantially the entire amount. consists of the above propylene- ⁇ -olefin copolymer and polyolefin resin. If the inorganic substance powder-filled resin composition does not substantially contain resin components other than the propylene- ⁇ -olefin copolymer and the polyolefin resin, it is particularly easy to select raw materials, composition and processing conditions.
  • the inorganic powder-filled resin composition of the present invention comprises, as thermoplastic resin components, a first resin that is a propylene- ⁇ -olefin copolymer and a second resin that is a different polyolefin resin. It contains at least two types of resin. Preferably the two resins are contained in a specific weight ratio.
  • the inorganic powder-filled resin composition of the present invention exhibits excellent physical properties in terms of both shape retention and flexibility, can be easily post-processed, and can be molded into molded articles with excellent impact resistance. becomes.
  • the first resin and the second resin are preferably mixed in an amount of 80 to 95 parts by mass: 20 to 5 parts by mass, more preferably 85 to 93 parts by mass: 15 to 7 parts by mass. , particularly preferably 87-92 parts by weight: 13-8 parts by weight. If the mass ratio of the first resin and the second resin is within the above range, it is possible to obtain an inorganic powder-filled resin composition having excellent balance between shape retention and flexibility. As a result, the inorganic powder-filled resin composition of the present invention becomes more suitable as a filament material for FDM.
  • the inorganic substance powder-filled resin composition of the present invention contains an inorganic substance powder together with the above thermoplastic resin.
  • the inorganic substance powder is not particularly limited. Specific examples include calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, silica, alumina, clays such as talc and kaolin, aluminum hydroxide, magnesium hydroxide, and silica.
  • the shape of the inorganic substance powder is not particularly limited, and may be in the form of particles, flakes, granules, fibers, or the like.
  • the particulate form it may be spherical as generally obtained by a synthetic method, or irregularly shaped as obtained by pulverizing collected natural minerals. .
  • These inorganic substance powders are preferably calcium carbonate, magnesium carbonate, dolomite, zinc oxide, titanium oxide, silica, alumina, clay, talc, kaolin, aluminum hydroxide, magnesium hydroxide and the like, particularly those containing calcium carbonate. is preferred.
  • the calcium carbonate may be either so-called light calcium carbonate prepared by a synthetic method or so-called heavy calcium carbonate obtained by mechanically pulverizing and classifying a natural raw material containing CaCO3 as a main component such as limestone. There may be one, or a combination of these may be used.
  • an inorganic substance powder containing heavy calcium carbonate is obtained by mechanically pulverizing and processing natural limestone or the like, and is clearly distinguished from synthetic calcium carbonate produced by chemical precipitation reaction or the like.
  • the pulverization method includes a dry method and a wet method, and the dry method is preferred.
  • Heavy calcium carbonate particles differ from light calcium carbonate produced by a synthetic method, and are characterized by surface irregularity and a large specific surface area due to the fact that the particles were formed by a pulverization process. Since the heavy calcium carbonate particles have such an irregular shape and a large specific surface area, when blended in a thermoplastic resin, the heavy calcium carbonate particles form a larger contact interface with the thermoplastic resin. It is effective for uniform dispersion.
  • the specific surface area of the heavy calcium carbonate particles is about 3,000 cm 2 /g or more and 35,000 cm 2 /g or less, depending on the average particle diameter. desired.
  • the specific surface area referred to here is obtained by the air permeation method. When the specific surface area is within this range, there is a tendency to suppress deterioration in processability of the obtained molded article.
  • the irregularity of the heavy calcium carbonate particles can be expressed by a low degree of spheroidization of the particle shape. 0.95 or less, more preferably 0.55 or more and 0.93 or less, and still more preferably 0.60 or more and 0.90 or less. If the roundness of the heavy calcium carbonate particles is within this range, the strength and moldability of the molded product will be moderate.
  • the circularity can be expressed by (the projected area of the grain)/(the area of the circle having the same circumferential length as the projected circumferential length of the grain).
  • the method for measuring the roundness is not particularly limited, and for example, the projected area and the projected peripheral length of the grain may be measured from a micrograph, or image analysis software that is generally commercially available may be used.
  • the surface may be surface-modified by a conventional method in order to enhance the dispersibility or reactivity of the inorganic substance powder.
  • surface-treated ground calcium carbonate can be preferably used.
  • surface modification methods include physical methods such as plasma treatment, and chemical surface treatment using a coupling agent or surfactant.
  • coupling agents include silane coupling agents and titanium coupling agents.
  • Surfactants may be anionic, cationic, nonionic or amphoteric, and examples thereof include higher fatty acids, higher fatty acid esters, higher fatty acid amides and higher fatty acid salts. On the contrary, it may contain inorganic substance powder that is not surface-treated.
  • the inorganic substance powder such as calcium carbonate particles is not particularly limited, but preferably has an average particle size of 0.5 ⁇ m or more and 9.0 ⁇ m or less, more preferably 0.7 ⁇ m or more and 6.0 ⁇ m or less. Preferably, it is 1.0 ⁇ m or more and 4.0 ⁇ m or less.
  • the average particle size of the inorganic substance powder described in this specification refers to a value calculated from the measurement result of the specific surface area by the air permeation method according to JIS M-8511.
  • a specific surface area measuring device SS-100 manufactured by Shimadzu Corporation can be preferably used.
  • the average particle size is larger than 9.0 ⁇ m, for example, when forming a sheet-like molded product, depending on the layer thickness of the molded product, the inorganic powder protrudes from the surface of the molded product, and the powder falls off. Otherwise, the surface properties, mechanical strength, etc. may be impaired.
  • the particle size distribution does not contain particles having a particle size of 45 ⁇ m or more.
  • the particles are too fine, the viscosity will increase significantly when kneaded with the above-mentioned resin, which may make it difficult to produce molded articles. Such a problem can be prevented by setting the average particle size of the inorganic powder to 0.5 ⁇ m or more, particularly 0.7 ⁇ m or more and 6.0 ⁇ m or less.
  • the calcium carbonate has an average particle size of 0.5 ⁇ m or more and less than 2.0 ⁇ m, particularly 0.7 ⁇ m or more and less than 2.0 ⁇ m, as measured by an air permeation method according to JIS M-8511.
  • the average particle size of the first calcium carbonate is a and the average particle size of the second calcium carbonate is b
  • the a/b ratio is 0.85 or less, more preferably. is roughly 0.10 to 0.70, more preferably 0.10 to 0.50. This is because a particularly excellent effect can be expected by jointly using particles having such a clear difference in average particle size to some extent.
  • each of the first calcium carbonate and the second calcium carbonate preferably has a coefficient of variation (Cv) of the distribution of particle diameters ( ⁇ m) of about 0.01 to 0.10, particularly 0.03. It is desirable to be about 0.08. If the variation in particle size defined by the coefficient of variation (Cv) is this level, it is considered that each powder group can provide more complementary effects.
  • the mass ratio of the first calcium carbonate to the second calcium carbonate is preferably about 90:10 to 98:2, more preferably about 92:8 to 95:5. Three or more calcium carbonate groups having different average particle size distributions may be used.
  • the first calcium carbonate and the second calcium carbonate are both surface-treated ground calcium carbonate.
  • the inorganic powder-filled resin composition of the present invention contains the thermoplastic resin and the inorganic powder in a mass ratio of 50:50 to 10:90. If the content of the inorganic substance powder is too small, the shrinkage rate and warpage during molding may not be improved.
  • the ratio of the inorganic substance powder to the total mass of the thermoplastic resin and the inorganic substance powder is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 75% by mass or more.
  • the upper limit of the ratio is preferably 87% by mass or less, more preferably 85% by mass or less, and particularly preferably 82% by mass or less.
  • the content of the first resin with respect to 100 parts by mass of the thermoplastic resin is set to 80 parts by mass or more and 95 parts by mass or less.
  • the amount is set to about 15 to 40% by mass, physical properties such as shape retention and flexibility can be improved in a well-balanced manner.
  • the inorganic powder-filled resin composition of the present invention becomes more suitable as a filament material for FDM.
  • additives can be added as auxiliary agents to the inorganic powder-filled resin composition according to the present invention.
  • Other additives include, for example, colorants, lubricants, coupling agents, fluidity modifiers (fluidity modifiers), cross-linking agents, dispersants, antioxidants, ultraviolet absorbers, flame retardants, stabilizers, and electrifying agents. Inhibitors, foaming agents, plasticizers, etc. may be blended. These additives may be used alone or in combination of two or more. Further, these may be blended in the kneading step described later, or may be blended in the raw material components in advance before the kneading step.
  • the addition amount of these other additives is not particularly limited as long as it does not impede the desired physical properties and processability.
  • each of these other additives is about 0 to 10% by mass, particularly about 0.04 to 5% by mass, and the total amount of the other additives is 10% by mass. % or less.
  • plasticizers include triethyl citrate, acetyl-triethyl citrate, dibutyl phthalate, diaryl phthalate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, di(2-ethylhexyl) phthalate, and di-phthalate. 2-methoxyethyl, dibutyl tartrate, o-benzoylbenzoate, diacetin, epoxidized soybean oil and the like. These plasticizers are usually blended in an amount of about several mass % with respect to the thermoplastic resin, but the amount is not limited to these ranges. It is also possible to In the inorganic powder-filled resin composition of the present invention, the blending amount is preferably about 0.5 to 10 parts by weight, particularly about 1 to 5 parts by weight, per 100 parts by weight of the thermoplastic resin.
  • organic pigments such as azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, diosazine-based, perinone-based, quinophthalone-based, and perylene-based pigments, ultramarine blue, titanium oxide, titanium yellow, and iron oxide. (Rouge), chromium oxide, zinc white, carbon black and other inorganic pigments.
  • lubricants include fatty acid-based lubricants such as stearic acid, hydroxystearic acid, complex stearic acid, and oleic acid; fatty alcohol-based lubricants; stearamide, oxystearamide, oleylamide, erucylamide, ricinolamide, behenamide, and methylol.
  • Aliphatic amide-based lubricants such as amides, methylenebisstearamide, methylenebisstearobehenamide, higher fatty acid bisamic acids, complex amides; n-butyl stearate, methyl hydroxystearate, polyhydric alcohol fatty acid esters, Fatty acid ester-based lubricants such as saturated fatty acid esters and ester-based waxes; fatty acid metal soap-based lubricants such as zinc stearate;
  • antioxidants phosphorus-based antioxidants, phenol-based antioxidants, and pentaerythritol-based antioxidants can be used.
  • Phosphorus-based, more specifically phosphorus-based antioxidant stabilizers such as phosphites and phosphates are preferably used.
  • phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and other phosphorous acid triesters, diesters, and monoesters. is mentioned.
  • Phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, and the like. These phosphorus-based antioxidants may be used alone, or two or more of them may be used in combination.
  • Phenolic antioxidants include ⁇ -tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2- t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-t-butyl-4-(N,N-dimethyl aminomethyl)phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane etc., and these can be used alone or in combination of two or more.
  • the flame retardant is not particularly limited, but for example, halogen flame retardants or non-phosphorus halogen flame retardants such as phosphorus flame retardants and metal hydrates can be used.
  • halogen flame retardants include halogenated bisphenol compounds such as halogenated bisphenylalkanes, halogenated bisphenyl ethers, halogenated bisphenylthioethers, and halogenated bisphenylsulfones, brominated bisphenol A, bromine Bisphenol-bis(alkyl ether) compounds such as bisphenol S, chlorinated bisphenol A, and chlorinated bisphenol S, and phosphorus-based flame retardants such as aluminum tris(diethylphosphinate) and bisphenol A bis(diphenyl phosphate).
  • triarylisopropyl phosphate cresyl di-2,6-xylenyl phosphate, aromatic condensed phosphate esters, etc.
  • metal hydrates such as aluminum trihydrate, magnesium dihydroxide, or combinations thereof. etc. can be exemplified, respectively, and these can be used alone or in combination of two or more. It works as a flame retardant assistant, and can improve the flame retardant effect more effectively.
  • antimony oxides such as antimony trioxide and antimony pentoxide, zinc oxide, iron oxide, aluminum oxide, molybdenum oxide, titanium oxide, calcium oxide, magnesium oxide, etc. can be used in combination as flame retardant aids. .
  • the foaming agent is mixed or pressurized into the inorganic substance powder-filled resin composition which is the raw material which is in a molten state in the melt kneader, and changes phase from solid to gas, liquid to gas, or gas itself, It is mainly used to control the foaming ratio (foaming density) of foamed sheets.
  • a foaming agent that is liquid at room temperature undergoes a phase change to a gas depending on the resin temperature and dissolves in the molten resin, while a foaming agent that is gas at room temperature does not undergo a phase change and dissolves in the molten resin as it is.
  • the foaming agent dispersed and dissolved in the molten resin expands inside the sheet as the pressure is released when the molten resin is extruded into a sheet from an extrusion die, forming a large number of fine closed cells within the sheet and foaming. A sheet is obtained.
  • the foaming agent secondarily acts as a plasticizer that lowers the melt viscosity of the raw material resin composition, and lowers the temperature for making the raw resin composition plasticized.
  • blowing agents include aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclobutane, cyclopentane and cyclohexane; chlorodifluoromethane, difluoromethane, trifluoromethane, trichlorofluoromethane; Methane, dichloromethane, dichlorofluoromethane, dichlorodifluoromethane, chloromethane, chloroethane, dichlorotrifluoroethane, dichloropentafluoroethane, tetrafluoroethane, difluoroethane, pentafluoroethane, trifluoroethane, dichlorotetrafluoroethane, trichlorotrifluoroethane , tetrachlorodifluoroethane and perfluorocyclobut
  • a carrier resin containing an active ingredient of the foaming agent can be preferably used.
  • carrier resins include crystalline olefin resins. Among these, crystalline polypropylene resins are preferred.
  • hydrogen carbonate etc. are mentioned as an active ingredient. Among these, hydrogen carbonate is preferred.
  • a blowing agent concentrate containing a crystalline polypropylene resin as a carrier resin and a hydrogen carbonate as a thermally decomposable blowing agent is preferred.
  • the content of the foaming agent contained in the foaming agent in the molding process can be appropriately set according to the amounts of the polyolefin resin, the propylene- ⁇ -olefin copolymer, and the inorganic substance powder. It is preferably in the range of 0.04 to 5.00% by mass relative to the total mass of the composition.
  • fluidity modifiers can also be used.
  • examples include, but are not limited to, peroxides such as dialkyl peroxides such as 1,4-bis[(t-butylperoxy)isopropyl]benzene and the like.
  • these peroxides may also act as crosslinkers.
  • the propylene- ⁇ -olefin copolymer has a diene-derived structural unit, a portion of the copolymer is crosslinked by the action of the peroxide, thereby controlling the physical properties and workability of the resin composition.
  • the amount of the peroxide to be added is not particularly limited, but it is in the range of 0.04 to 2.00% by mass, particularly 0.05 to 0.50% by mass, based on the total mass of the resin composition filled with the inorganic powder. preferably.
  • antistatic agents it is possible to use, for example, fatty acid diethanolamides such as lauryl diethanolamide and stearyl diethanolamide, hydroxyl group-containing compounds such as alcohol amine compounds, and the like. Alcohol amines such as monoethanolamine, diethanolamine, triethanolamine and the like are particularly preferred. Two or more antistatic agents can be used in combination. These antistatic agents may be supported on calcium silicate, calcium carbonate, or the like. It should be noted that the number of carbon atoms in the acyl group of the fatty acid diethanolamide is preferably in the range of about 8 to 22 from the viewpoint of exhibiting a sufficient antistatic effect.
  • the amount of such an antistatic agent is about 0.01 to 8.00% by mass, more preferably 0.02%, when the total mass of the inorganic powder-blended thermoplastic resin composition is 100% by mass. It is desired that the content be blended in a proportion of up to 4.00% by mass, more preferably 0.05 to 3.00% by mass, particularly about 0.10 to 1.50% by mass. By using it within this range, in addition to obtaining a sufficient antistatic effect, there is little possibility that the surface of the resin will become sticky or that the physical properties of the resin will be adversely affected.
  • the present invention also provides an inorganic substance powder-filled resin composition for fused lamination method 3D printer filaments containing a thermoplastic resin and an inorganic substance powder at a mass ratio of 50:50 to 10:90, wherein the thermoplastic
  • the resin contains a first resin and a second resin, the first resin is a propylene- ⁇ -olefin copolymer, and the second resin is a polyolefin resin different from the first resin.
  • the content of the first resin is 80 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. composition.
  • Such a resin composition exhibits good shape retention as described above, is flexible and can be easily post-processed, and is therefore suitable as a filament material for FDM.
  • the inorganic powder-filled resin composition of the present invention may have any physical properties depending on the desired shaped article, but from the viewpoint of improving the shaping accuracy, the density is 1.40 to 2.2 g. /cm 3 (JISK7112), melt flow rate 0.5-4.0g/10min (230°C, 2,16kg JISK7210), tensile yield stress 10-2.2MPa (JISK7161), tensile modulus 2500-5000MPa ( JISK7161) is preferable.
  • a resin composition having such physical properties can be easily molded and exhibits sufficient strength.
  • a method for producing the inorganic powder-filled resin composition of the present invention a conventional method can be used, and it may be appropriately set according to the molding method (extrusion molding, injection molding, vacuum molding, etc.).
  • the first resin, the second resin, and the inorganic substance powder may be kneaded and melted before being put into the molding machine from the hopper, and the first resin, the second resin, and the inorganic powder may be melted together with the molding machine at the same time as molding.
  • the substance powder may be kneaded and melted. Melt-kneading is preferably carried out by applying a high shear stress while dispersing each component uniformly.
  • a mixing device various devices such as a general extruder, a kneader, and a Banbury mixer can be used.
  • the kneading order of the first resin, the second resin, and the inorganic substance powder there is no particular limitation on the kneading order of the first resin, the second resin, and the inorganic substance powder.
  • these three materials can be kneaded at the same time, or after kneading the first resin and the second resin, the thermoplastic resin mixture and the inorganic substance powder can be kneaded.
  • An inorganic powder may be kneaded into each of the first resin and the second resin, and the two thermoplastic resins may be kneaded after the melt viscosities of the two types of thermoplastic resins are made uniform. It is also possible to knead the first resin and the inorganic substance powder once and then knead the second resin.
  • the inorganic powder-filled resin composition may be in the form of pellets or may not be in the form of pellets.
  • the shape of is not particularly limited, and for example, pellets in the shape of a cylinder, a sphere, or an ellipsoid may be formed.
  • the size of the pellet may be appropriately set according to the shape, but for spherical pellets, for example, the diameter may be 1 to 10 mm. In the case of an elliptical pellet, it may be elliptical with an aspect ratio of 0.1 to 1.0 and a length and width of 1 to 10 mm. In the case of cylindrical pellets, the diameter may be in the range of 1 to 10 mm and the length in the range of 1 to 10 mm. These shapes may be molded into the pellets after the kneading process described below. The shape of pellets may be formed according to a conventional method.
  • a molded article according to the present invention is a molded article made of the inorganic powder-filled resin composition described above.
  • the shape and the like of the molded product according to the present invention are not particularly limited, and various shapes may be used.
  • it can be a sheet having a thickness of 40 ⁇ m to 20 mm, particularly about 50 ⁇ m to 1,000 ⁇ m, various shapes of containers, housings, daily necessities, and various other extruded or injection molded products.
  • the method for producing the molded article of the present invention is not particularly limited as long as it can be molded into a desired shape, and any of conventionally known methods such as extrusion molding, injection molding, vacuum molding, blow molding and calendar molding can be used. Can be molded. Furthermore, even in the case where the inorganic substance powder-filled resin composition according to the present invention contains a foaming agent and a molded article in the form of a foam is obtained, the molding method of the foam can be used as long as it can be molded into a desired shape. For example, conventionally known liquid phase foaming methods such as injection foaming, extrusion foaming, and foam blowing, or solid phase foaming methods such as bead foaming, batch foaming, press foaming, and normal pressure secondary foaming are used.
  • thermoplastic composition containing crystalline polypropylene as a carrier resin and a hydrogen carbonate as a thermally decomposable foaming agent an injection foaming method and an extrusion foaming method can be desirably used.
  • Molded articles of the present invention are preferably extruded articles. Examples include, but are not limited to, articles of various shapes such as sheets, rods, pipes, tubes, strands, and the like.
  • the extrusion molding method is not particularly limited, and general-purpose methods such as single-screw extrusion and twin-screw extrusion can be used.
  • a direct method in which the step of kneading each component and the step of forming into a sheet or the like are continuously performed may be used.
  • a method using a T-die type twin-screw extruder may be used. .
  • the molded sheet When it is molded into a sheet, it can be stretched uniaxially, biaxially, or multiaxially (such as by tubular stretching) during or after molding. In the case of biaxial stretching, sequential biaxial stretching or simultaneous biaxial stretching may be used.
  • biaxial stretching sequential biaxial stretching or simultaneous biaxial stretching may be used.
  • minute voids are generated in the sheet. The whiteness of the sheet is improved by the formation of minute voids in the sheet.
  • the molding temperature in injection molding, extrusion molding, etc. varies to some extent depending on the molding method and the type of polypropylene resin used, so it cannot be defined unconditionally.
  • the inorganic powder-filled resin composition according to the present invention has good drawdown properties and spreadability, and the composition does not locally denature. It can be molded into a predetermined shape.
  • the molded article of the present invention is particularly preferably a fused layered 3D printer filament.
  • the FDM filament of the present invention has the advantages of suppressing heat shrinkage and warping during molding, exhibiting good shape retention, being flexible, easy to post-process, excellent in molding accuracy, and having high impact resistance. .
  • the diameter of the filament for FDM of the present invention can be arbitrarily set according to the capacity of the manufacturing apparatus used for molding the resin molding by the hot melt lamination method.
  • the lower limit of the diameter is preferably 0.5 mm or more, more preferably 1.0 mm or more, and particularly preferably 1.5 mm or more, while the upper limit is preferably 5.0 mm or less, more preferably 4.0 mm. Below, more preferably 3.5 mm or less, particularly preferably 3.0 mm or less. Since the resin composition of the present invention generally has a high specific gravity, it is possible to form thin filaments for FDM.
  • the accuracy of the FDM filament diameter should be within ⁇ 5% for any measurement point of the filament.
  • the FDM filament of the present invention preferably has a diameter standard deviation of 0.07 mm or less, particularly 0.06 mm or less. The standard deviation can be obtained by measuring the major and minor diameters of filaments at 10 points at intervals of 3 cm with vernier calipers.
  • the FDM filament of the present invention preferably has a circularity of 0.93 or more, particularly 0.95 or more.
  • the upper limit of circularity is 1.0.
  • the filament is measured at 10 points at intervals of 3 cm, the major axis and minor axis are measured with a vernier caliper, the minor axis / major axis ratio at each measurement point is obtained, and the minor axis / major axis at the measured 10 points.
  • the average of the ratios can be taken as the circularity.
  • the FDM filament of the present invention preferably has an elongation at break of 30% or more, and an elongation of 100% or more improves the toughness of the filament and prevents the filament from breaking when the filament is incorporated.
  • the upper limit of this breaking strain is not particularly set, it is usually about 1000%.
  • the method for producing the FDM filament of the present invention is not particularly limited, but the inorganic substance powder-filled resin composition of the present invention can be molded by a known molding method such as extrusion molding, or the filament can be formed as it is during the production of the resin composition. It can be obtained by a method such as For example, the resin composition can be kneaded under the extrusion conditions as described above and at the same time formed into a filament to form the filament for FDM of the present invention.
  • ⁇ Filament roll and cartridge> When producing a resin molded product by a three-dimensional printer using the filament for FDM of the present invention, it is usually closed and packaged as a wound body wound on a bobbin, or the wound body is stored in a cartridge. This is preferable from the viewpoints of long-term storage, stable delivery, protection from environmental factors such as humidity, and prevention of twisting.
  • the cartridge include a wound body wound on 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.
  • Example 1 Pellets of the inorganic powder-filled resin composition were prepared using the following raw materials, and test pieces such as filaments were formed from the pellets and subjected to various evaluation tests.
  • R1-1 first resin
  • vistamaxx® 6502 an ethylene-propylene copolymer from ExxonMobil Corporation (density 0.865 g/cm 3 )
  • second resin propylene homopolymer manufactured by Prime Polymer Co., Ltd. (MFR: 0.5 g/10 min)
  • CC1 Heavy calcium carbonate manufactured by Bihoku Funka Kogyo Co., Ltd. (no surface treatment) Average particle size: 2.2 ⁇ m, BET specific surface area: 1.0 m 2 /g, circularity: 0.85 ⁇ Lubricant: magnesium stearate
  • the pellets were introduced into a twin-screw kneading extruder with a screw diameter of 15 mm to produce filaments.
  • the twin-screw kneading extruder has a set temperature of 200 ° C. and a discharge rate of 1.0 kg / hr, extruding the resin composition from a die diameter of 3 mm, passing through a water tank of 40 ° C. and taking it off at 5 m / min with a take-up device. rice field.
  • the cross-sectional diameters of the resulting filaments ranged from 1.65 mm to 1.90 mm.
  • the filament obtained above is introduced into a fused layer deposition method 3D printer "BLADE-1" manufactured by Hot Proceed Co., Ltd., and a cup-shaped molded body 1 (three-dimensional modeled object) having an upper opening is formed. rice field.
  • the manufacturing conditions were a standard mode, a printing speed of 150 mm/sec, a substrate temperature of 60°C and an ejection temperature of 200°C.
  • the molten resin was extruded from the extrusion head in strands with a diameter of 0.1 mm.
  • a test piece of 80 mm ⁇ 10 mm ⁇ 1 mm was injection molded from the pellet, and the appearance of the test piece was observed to evaluate the degree of thermal shrinkage. Moreover, the following flexibility (flexibility) test was performed using the same test piece.
  • the above test piece was folded by hand and evaluated for flexibility according to the following criteria.
  • ⁇ A The test piece was bent five times up to about 160°, but did not break.
  • ⁇ The test piece was not broken unless it was bent two or three times to about 160°.
  • Examples 2-3, Comparative Examples 1-3 The same operation as in Example 1 was performed while changing the blending amounts of the raw materials as shown in Table 1. Evaluation results are shown in Table 1 below.
  • Example 5-6 The same operation as in Example 1 was performed using commercially available polylactic acid (PLA) and ABS resin. The evaluation results are shown in Table 1 below together with the composition of each sample.
  • thermoplastic resin and an inorganic substance powder are contained in a mass ratio of 50:50 to 10:90, and a propylene- ⁇ -olefin copolymer as the first resin and polypropylene as the second resin and the content of the first resin is 80 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. and heat-shrinkability, and proved to be suitable as a filament material for FDM. It was also found that the inorganic powder-filled resin composition according to the present invention exhibits high flexibility and is a material with excellent flexibility.
  • Comparative Example 1 in which the content of the first resin was outside the range defined by the present invention, the resin composition became hard, and post-processability and flexibility decreased.
  • the resin composition of Comparative Example 2 which did not contain the second resin, had good flexibility, but was unsuitable as a filament material for FDM in terms of reproducibility and heat shrinkability.
  • the same results as in Comparative Example 2 were obtained even with the resin composition of Comparative Example 3, which contained a small amount of inorganic substance powder.
  • resin compositions containing polylactic acid and ABS resin are inferior in flexibility, reproducibility, and the like.
  • Examples 4-7, Comparative Examples 7-10 A sample having the composition shown in Table 2 was prepared in the same manner as in Example 1 using the following raw materials.
  • R1-2 first resin: vistamaxx® 6102, an ethylene-propylene block copolymer from ExxonMobil Corporation (ethylene content 16%, density 0.862 g/cm 3 )
  • second resin propylene homopolymer manufactured by Prime Polymer Co., Ltd.
  • MFR 2.0 g / 10 min
  • R2-3 second resin
  • MFR 55 g / 10 min
  • ⁇ CC2 Maruo Calcium Co., Ltd.
  • melt flow rate (MFR) and Charpy impact strength were measured by the following methods. Table 2 shows the composition of each sample and the test/evaluation results.
  • MFR Measured under the conditions of 230°C and 2.16 kg.
  • Charpy impact strength A test piece of 80 mm x 10 mm x 1 mm was used and measured according to ISO179/1eA.
  • the present invention contains a propylene- ⁇ -olefin copolymer as the first resin and polypropylene as the second resin, and the content of the first resin is 80 parts per 100 parts by mass of the thermoplastic resin.
  • the MFR also showed a moderate value, and it was found to be excellent in workability and suitable as a filament material for FDM.
  • the inorganic powder-filled resin compositions of Examples 4-7 according to the present invention also exhibited excellent flexibility, high flexibility and Charpy impact strength.

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Abstract

La présente invention aborde le problème consistant à fournir : une composition de résine chargée d'une poudre de substance inorganique qui est appropriée en tant que matériau de filament FDM, présente une contraction thermique inhibée, etc., et est flexible avec une excellente résistance aux chocs ; une composition de résine chargée d'une poudre de substance inorganique pour un filament d'imprimante 3D de modélisation par dépôt de matière fondue ; et un filament d'imprimante 3D de modélisation par dépôt de matière fondue.　La présente invention concerne une composition de résine chargée d'une poudre de substance inorganique contenant une résine thermoplastique et une poudre de substance inorganique selon un rapport de masse variant de 50/50 à 10/90, la composition de résine chargée d'une poudre de substance inorganique étant caractérisée en ce que la résine thermoplastique contient une première résine et une seconde résine, la première résine consiste en un copolymère de propylène-α-oléfine, la seconde résine consiste en une résine de polyoléfine différente de la première résine, et la teneur en première résine varie de 80 à 95 parties en masse pour 100 parties en masse de la résine thermoplastique.
PCT/JP2022/030749 2021-11-25 2022-08-12 Composition de résine chargée d'une poudre de substance inorganique et produit moulé WO2023095393A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7496927B1 (ja) 2023-10-26 2024-06-07 第一セラモ株式会社 ３ｄプリンタのフィラメント用組成物、３ｄプリンタ用フィラメント、焼結体、及び焼結体の製造方法

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