JP2017209969A - Material for three-dimensional molding, method for manufacturing three-dimensional molded object, and apparatus for manufacturing three-dimensional molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material for three-dimensional molding, which gives a three-dimensional molded object having high accuracy and little warpage and facilitating a post process such as surface polishing.SOLUTION: The material for three-dimensional molding comprises a thermoplastic resin and planar inorganic particles having an organic metal oxide group on the surfaces thereof, in order to manufacture a three-dimensional molded object using an apparatus 1 for manufacturing a three-dimensional molding, with a heating head 13 for melting and discharging the material for three-dimensional molding. In preferred embodiments, the metal in the organic metal oxide group is one of Si, Ti, and Al; and the organic metal oxide group is at least one of alkoxy silane, alkoxy titanium, and alkoxy aluminum. Preferably, the planar inorganic particles are at least one compound selected from metal oxide, inorganic sheet silicate, and swellable clay mineral substituted with an organic substance; and the particles have a major axis average particle diameter of 1 to 3 μm and an aspect ratio of 10 to 1000, and are included by 1 to 10 mass%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a three-dimensional modeling material, a three-dimensional model manufacturing method, and a three-dimensional model manufacturing apparatus.

  Conventionally, in fields such as medical treatment, architecture, and manufacturing, three-dimensional modeling techniques have been used for the purpose of obtaining products and parts having desired shapes. As this three-dimensional modeling technique, a 3D printing technique is known in which modeling materials are arranged in three dimensions based on CAD (computer aided design) data.

  One of the 3D printing technologies, the three-dimensional modeling technology based on the Fused Deposition Modeling (FDM), heats a filamentous resin composition called a model material via a conveyance tube by a conveyance gear. It is conveyed to the head, melted and discharged to form a layer having a predetermined shape. Furthermore, by repeating this operation, the model material is laminated to obtain a desired three-dimensional shaped object.

As the FDM model material, for example, a styrene resin obtained by copolymerizing an aromatic vinyl monomer and a vinyl cyanide monomer with a polylactic acid resin, and a glass transition temperature of 20 ° C. or less. A resin composition in which a thermoplastic resin and a plasticizer are blended has been proposed (see, for example, Patent Document 1).
Moreover, a resin composition in which a functional nanofiller is dispersed in a thermoplastic resin has been proposed (see, for example, Patent Document 2).

  An object of the present invention is to provide a material for three-dimensional modeling that can obtain a three-dimensional modeled object that is highly accurate, has little warpage, and is easily post-processed such as surface polishing.

  The three-dimensional modeling material of the present invention as a means for solving the above-described problems contains a thermoplastic resin and plate-like inorganic particles having an organometallic oxide group on the surface.

  According to the present invention, it is possible to provide a material for three-dimensional modeling that can obtain a three-dimensional modeled object that is highly accurate, has little warpage, and can be easily subjected to post-processing such as surface polishing.

FIG. 1 is a schematic diagram illustrating an example of a three-dimensional object manufacturing apparatus of the present invention used in the method for manufacturing a three-dimensional object of the present invention. FIG. 2A is a plan view illustrating an example of a three-dimensional object formed using the three-dimensional object material of the present invention. FIG. 2B is a cross-sectional view taken along line AA of the three-dimensional structure in FIG. 2A. FIG. 2C is a schematic cross-sectional view illustrating an example of a step of removing the support of the three-dimensional structure illustrated in FIG. 2B. FIG. 3 is a drawing showing a three-dimensional structure produced in the example.

(Three-dimensional modeling material)
The material for three-dimensional modeling of the present invention contains a thermoplastic resin and plate-like inorganic particles having an organometallic oxide group on the surface, and preferably contains an organometallic compound. Contains ingredients.

The three-dimensional modeling material is a material used when a three-dimensional model is manufactured by the hot melt lamination method (FDM), and may be referred to as “three-dimensional modeling filament”, “three-dimensional modeling strand”, or the like.
The “filament” or “strand” means, for example, a material obtained by extruding a resin composition containing a thermoplastic resin into a string shape or a thread shape.

As the FDM model material, polylactic acid resin (PLA) and acrylonitrile-butadiene-styrene copolymer resin (ABS) are mainly used.
The ABS is excellent in impact resistance, rigidity, and heat resistance, has appropriate chemical resistance, and is excellent in post-processing properties such as polishing, but there is a problem that warping is likely to occur in a molded article. is there.
Although the PLA does not warp in the molded article, it is inferior in durability, impact resistance, and heat resistance compared to the ABS, and has a problem that post-processability such as surface polishing is inferior because it is not sticky and hard. .
In order to prevent warping of the modeled object in the ABS, measures such as raising the ambient temperature during modeling to be higher than room temperature are taken. There is a demand for a material that is less likely to warp and can be easily post-treated such as surface polishing.

  The material for three-dimensional modeling of the present invention is a styrene resin obtained by copolymerizing an aromatic vinyl monomer and a vinyl cyanide monomer with a conventional polylactic acid resin. It is inferior in post-processability such as surface polishing because it is used, and in the resin composition in which the functional nanofiller is dispersed in the conventional thermoplastic resin, the quality is unstable because the dispersion of the functional nanofiller is not stable. It is based on the knowledge that it is.

Therefore, in the material for three-dimensional modeling of the present invention, when the plate-like inorganic particles having an organometallic oxide group on the surface are added to and mixed with the thermoplastic resin, the plate-like inorganic particles are stable in the thermoplastic resin. It acts as a wedge that is dispersed in the resin and connects the resin molecules, and the thermal shrinkage that occurs when the thermoplastic resin is cooled and solidified can be reduced to prevent warping.
Further, the plate-like inorganic particles act as crystal nuclei when the thermoplastic resin is cooled and solidified, and improve the sharp melt property of the thermoplastic resin. Can be improved.
Furthermore, the plate-like inorganic particles act as a lubricant and can improve post-processability such as surface polishing.

<Thermoplastic resin>
The thermoplastic resin means a resin that becomes soft when heated to a glass transition temperature or a melting point and can be molded into a desired shape.
The thermoplastic resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylonitrile-butadiene-styrene copolymer resin (ABS), polylactic acid resin (PLA), polyamide resin (PA), Polyester resins such as polypropylene resin (PP), polyethylene resin (PE), polycarbonate resin (PC), polyvinyl chloride resin, acrylic resin, polystyrene resin (PS), polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT) Polyurethane resin, polyphenylene ether resin, polyacetal resin, polyphenylene sulfide resin, fluorine resin, polyamideimide resin, polyethersulfone resin, polysulfone resin, liquid crystal polymer, polyarylate resin, polyether resin De resin (PEI), polyether ether ketone resin (PEEK) aromatic and polyether ketone resins, ethylene - propylene - diene rubber (EPDM) thermoplastic resin elastomers such as rubber, or the like of these alloys and the like. These may be used individually by 1 type and may use 2 or more types together.
As said thermoplastic resin, what was synthesize | combined suitably may be used and a commercial item may be used.

<Plate-like inorganic particles>
The plate-like inorganic particles are preferably at least one selected from organic substitutes of metal oxides, inorganic layered silicates, and swellable clay minerals, having an organometallic oxide group on the surface.

  Examples of the metal oxide include alumina, silica, titanium dioxide (titania), zirconium dioxide (zirconia), tin oxide, and zinc oxide. These may be used individually by 1 type and may use 2 or more types together.

Examples of the inorganic layered silicate include montmorillonite, smectite, illite, sepiolite, allelevaldite, amesite, hectorite, talc, fluorohectorite, saponite, beidellite, nontronite, stevensite, bentonite, mica, Examples include fluoromica, vermiculite, fluorovermiculite, and halloysite. These may be used individually by 1 type and may use 2 or more types together.
In the crystal structure of the inorganic layered silicate, SiO ₄ tetrahedrons are planarly connected by a covalent bond, and the planar strength is high. Moreover, since the particles are easily peeled between layers, the particles have a high aspect ratio, and a high improvement effect can be expected.

As the organic substitute for the swellable clay mineral, for example, organic substitutes for the swellable clay mineral such as montmorillonite, smectite, saponite, hectorite, and synthetic mica are preferable.
When the organic-substitution product of the swellable clay mineral is added to and mixed with the thermoplastic resin, the resin molecules are taken in between the layers of the swellable clay mineral, and can be sliced and dispersed stably in the thermoplastic resin.
The organic substance to be substituted is not particularly limited as long as it is an organic cation, and can be appropriately selected according to the purpose. From the viewpoint of high affinity with a thermoplastic resin, dimethylalkylammonium, dimethyldialkylammonium, benzyl Quaternary ammonium such as ammonium and alkylbis (2-hydroxyethyl) methylammonium is preferred.

-Organometallic oxide group-
The organometallic oxide group means an organometallic oxide group having an oxygen-containing organic group at the terminal.
The metal in the organometallic oxide group is preferably any of silicon (Si), titanium (Ti), and aluminum (Al).
The organometallic oxide group is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of high binding properties with the plate-like inorganic particles, alkoxysilane, alkoxytitanium, and Any of the alkoxyaluminums is preferred.
It is analyzed by XPS (X-ray photoelectron spectrometer), FT-IR (Fourier transform infrared spectrophotometer), etc. that the said plate-like inorganic particle has an organometallic oxide group on the surface. be able to.

-Method of forming organometallic oxide groups on the surface of plate-like inorganic particles-
The method for forming the organometallic oxide group on the surface of the plate-like inorganic particles is not particularly limited and can be appropriately selected according to the purpose. Broadly speaking, there are a dry processing method and a wet processing method. .
Examples of the dry treatment method include a direct treatment method in which a coupling agent is directly added while stirring the plate-like inorganic particles with a Henschel mixer or the like, and a primer method in which a coupling agent is directly applied to the surface of the plate-like inorganic particles. And an integral blend method in which a matrix resin, the plate-like inorganic particles, and a coupling agent are added during kneading and kneaded to form a composite.
Examples of the wet processing method include a slurry method in which the plate-like inorganic particles and the coupling agent are stirred and mixed in a solvent, followed by filtration and drying.

  As said coupling agent, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent etc. are mentioned, for example. These may be used individually by 1 type and may use 2 or more types together. Among these, a silane coupling agent is particularly preferable.

  Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, and N- (2-aminoethyl) aminopropyl. Methyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (amino Ethyl) -3-aminopropylto Methoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (1,3-dimethyl-butylidene) -propylamine, N -Phenyl-3-aminopropyltrimethoxysilane, N, N-bis (3- (trimethoxysilyl) propyl) ethylenediamine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1- Propanamine, 3-phenylaminopropyltrimethoxysilane, aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (2- (vinylbenzamino) ethyl) -3-aminopropyltrimethoxysilane hydrochloride, 1,2-ethanediamine, N- {3- (trimethoxysilyl) propyl Pill} -N-{(ethenylphenyl) methyl} derivative / hydrochloride, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

  The addition amount of the coupling agent is preferably 1% by mass or more and 3% by mass or less with respect to the plate-like inorganic particles.

The long axis average particle diameter of the plate-like inorganic particles is preferably 1 μm or more and 3 μm or less.
The major axis particle size means the longest axis length among the XYZ axis lengths of the particle shape of the plate-like inorganic particles.
The major axis average particle diameter can be measured by, for example, SEM observation, optical microscope observation, a laser diffraction particle size distribution measuring device, or the like.
The aspect ratio of the plate-like inorganic particles is preferably 10 or more and 1,000 or less, and more preferably 20 or more and 100 or less.
The aspect ratio can be calculated, for example, by measuring the particle average thickness by cross-sectional SEM observation, TEM observation, SPM (scanning probe microscope) measurement, and the like, and dividing the major axis average particle diameter by the particle average thickness. .
When the major axis average particle size is 1 μm or more and the aspect ratio is 10 or more, the action as a wedge connecting the molecules of the thermoplastic resin is appropriate. Moreover, when the said long axis average particle diameter is 3 micrometers or less, the dimensional accuracy and external appearance of a three-dimensional molded item are favorable. Furthermore, when the aspect ratio is 1,000 or less, the strength of the plate-like inorganic particles themselves is appropriate, and the effect as a wedge for connecting the molecules of the thermoplastic resin is good.

  1 mass% or more and 10 mass% or less are preferable with respect to the whole quantity of the three-dimensional modeling material, and, as for content of the said plate-shaped inorganic particle, 3 mass% or more and 5 mass% or less are more preferable. When the content is 1% by mass or more, the number of plate-like inorganic particles present in the thermoplastic resin is appropriate, and a sufficient effect can be obtained. Moreover, the distance between the plate-like inorganic particles in a thermoplastic resin is appropriate in the said content being 10 mass% or less, and a favorable improvement effect is acquired.

<Organic metal compound>
The organometallic compound is contained in order to improve the interfacial affinity between the thermoplastic resin and the plate-like inorganic particles and improve the dispersion stability.
The organometallic compound is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include metal soaps such as a stearic acid metal salt, a lauric acid metal salt, a ricinoleic acid metal salt, and an octylic acid metal salt. Can be mentioned.
The content of the organometallic compound is preferably 1% by mass or more and 5% by mass or less with respect to the total amount of the three-dimensional modeling material.

<Other ingredients>
The other components are not particularly limited and can be appropriately selected depending on the purpose. For example, plasticizers, fillers, reinforcing agents, stabilizers, dispersants, antioxidants, flame retardants, foaming agents, Examples thereof include antistatic agents, lubricants, colorants, and various polymer modifiers.

<Method for manufacturing material for three-dimensional modeling>
There is no restriction | limiting in particular in the three-dimensional modeling material of this invention, It can manufacture using the conventionally well-known extrusion method.
The extrusion molding is a long plastic article having a predetermined cross-sectional shape by extruding the thermoplastic resin, the plate-like inorganic particles, and, if necessary, the resin composition containing the other components while melt-kneading. Is a continuous molding method.
After melt-mixing the thermoplastic resin, the plate-like inorganic particles, and, if necessary, the other components, using a single-screw extruder while melting, extruding into a filament shape, and using a winder while cooling It can be manufactured by winding on a bobbin or the like.
The diameter of the filament can be controlled by an extrusion hole of a single screw extruder, temperature conditions, tension conditions at the time of winding, and the like. In addition, after cooling, the filament can be drawn by adjusting the tension condition during winding while further heating.

  The melt mixing method is not particularly limited, and a known method can be appropriately selected according to the purpose. Each component is continuously melted by a twin screw extruder, a single screw extruder, a melt molding machine, or the like. A method of mixing, a method of melting and mixing for each batch with a kneader, a mixer or the like can be mentioned. When the additive is not contained, the melt mixing step can be omitted.

Examples of the shape of the three-dimensional modeling material include a filament shape, a tablet shape, and a particle shape.
There is no restriction | limiting in particular as a diameter of the said filament shape, Although it can select suitably according to the objective, 1 mm or more and 5 mm or less are preferable, and 1.7 mm or more and 3 mm or less are more preferable.

(Manufacturing method and three-dimensional object manufacturing apparatus for three-dimensional object)
The manufacturing method of the three-dimensional molded item of this invention manufactures a three-dimensional molded item using the said three-dimensional modeling material of this invention.
The three-dimensional object manufacturing apparatus of the present invention includes the three-dimensional object material of the present invention,
A heating head that melts and discharges the three-dimensional modeling material, and further includes other means as necessary.

  The three-dimensional structure forming material may be a three-dimensional structure forming material (model material), a support body forming material (support material), or both.

  The three-dimensional structure manufacturing apparatus, for example, based on the input three-dimensional shape data, heat-melts the three-dimensional structure material of the present invention including the thermoplastic resin, and discharges it to an arbitrary position ( A nozzle head) and means for depositing the discharged three-dimensional modeling material of the present invention (modeling stage), and further includes other means as necessary. Specifically, a known hot melt lamination method (FDM) type three-dimensional structure manufacturing apparatus (three-dimensional (3D) printer) is preferably used.

The three-dimensional object manufacturing apparatus conveys the three-dimensional object material of the present invention from the three-dimensional object material supply unit toward the heating head at a predetermined speed, and the three-dimensional object material is heated and melted in the heating head. , Discharged at an arbitrary position. The discharged three-dimensional modeling material is deposited on a modeling stage. When these series of operations are finished, the modeling stage is lowered, and the three-dimensional modeling material discharged from the heating head is laminated by repeating the same operation, and a three-dimensional modeled object can be manufactured.
The heating temperature of the heating head is not particularly limited as long as the three-dimensional modeling material can be melted, and can be appropriately selected according to the purpose, but the thermoplastic resin contained in the three-dimensional modeling material is decomposed. It is preferred not to exceed the temperature. When the decomposition temperature of the thermoplastic resin is exceeded, nozzle clogging occurs due to the decomposition product, leading to a decrease in modeling stability.

The heating head can be effectively provided with a heating means so that the three-dimensional modeling material is not peeled off during modeling. The heating temperature is not particularly limited as long as the material for three-dimensional modeling does not peel off from the modeling stage during modeling, or the three-dimensional model does not melt and deform on the modeling stage, and can be appropriately selected according to the purpose. Although it is, it is preferable that it is more than the glass transition temperature of the said thermoplastic resin contained in the three-dimensional modeling material. In addition, a method of sticking a sheet, a sticker or the like for improving the adhesion with the filament material on the modeling stage is also effective. However, if the adhesiveness is too strong, it may be difficult to take out the three-dimensional model after the modeling is finished.
Since the three-dimensional modeling material is for directly producing a three-dimensional modeled object, a model material made of the water-insoluble thermoplastic resin is generally used, but a water-soluble support material made of the thermoplastic resin is used. It is also possible to model.

  On the other hand, the support material is originally used to support modeling by the model material. Therefore, when manufacturing a three-dimensional molded item, a three-dimensional molded item manufacturing apparatus having at least two nozzle heads for a model material and a support material is usually used. Thus, after producing the three-dimensional molded item which consists of a model material and a support material, the three-dimensional molded item which consists of a model material can be obtained by removing only a support material.

FIG. 1 is a schematic diagram illustrating an example of a three-dimensional structure manufacturing apparatus (three-dimensional (3D) printer) 1 of a hot melt lamination method (FDM) method.
The three-dimensional structure manufacturing apparatus 1 includes a chamber 3 inside a main body frame 2. The inside of the chamber 3 is a processing space for modeling a three-dimensional structure, and a stage (base) 4 as a mounting table is provided in the processing space, that is, inside the chamber 3. A three-dimensional model is modeled on the stage 4.

  A heating head 13 as a modeling means is provided above the stage 4 inside the chamber 3. The heating head 13 has a filament that is a modeling material for a three-dimensional model (hereinafter also referred to as “model material”) and a support modeling material (hereinafter also referred to as “support material”). It has the injection nozzle 11 which injects. Four injection nozzles 11 are provided on the heating head 13, but the number of injection nozzles 11 is arbitrary. Further, the heating head 13 is provided with a head heating unit 12 which is a modeling material heating unit as a heating unit for heating the filament supplied to each injection nozzle 11.

  The filament has an elongated wire shape, is set in the three-dimensional object manufacturing apparatus 1 in a wound state, and is supplied to each injection nozzle 11 on the heating head 13 by the filament supply unit 6. The filament may be the same for each injection nozzle 11 or may be different. The filament supplied from the filament supply unit 6 is heated and melted by the head heating unit 12 and the melted filament is ejected from the predetermined injection nozzle 11 to form a three-dimensional object layer on the stage 4. And by repeating this, a three-dimensional molded item is modeled.

  Note that the injection nozzle 11 on the heating head 13 is supplied with a support forming material (support material) that does not constitute a three-dimensional object, instead of a three-dimensional object. This support material is usually formed of a material different from the filament of the modeling material, and finally removed from the three-dimensional structure formed of the filament. This support material is also heated and melted by the head heating unit 12 and injected so that the molten support material is pushed out from the predetermined injection nozzle 11 to form a support layer.

  The heating head 13 is held movably along the longitudinal direction (X-axis direction) of the X-axis drive mechanism 21 via a connecting member with respect to the X-axis drive mechanism 21 extending in the left-right direction of the apparatus. The heating head 13 can be moved in the left-right direction of the apparatus (X-axis direction) by the driving force of the X-axis drive mechanism 21. Since the heating head 13 is heated to a high temperature by the head heating unit 12, it is preferable that the connecting member has a low heat conductivity so that the heat is not easily transmitted to the X-axis drive mechanism 21.

  Both ends of the X-axis drive mechanism 21 are slidably held along the longitudinal direction (Y-axis direction) of the Y-axis drive mechanism 22 with respect to the Y-axis drive mechanism 22 extending in the front-rear direction of the apparatus. When the X-axis drive mechanism 21 is moved along the Y-axis direction by the driving force of the Y-axis drive mechanism 22, the heating head 13 can be moved along the Y-axis direction.

  On the other hand, the stage 4 is fixed to the main body frame 2 and is held so as to be movable along the longitudinal direction of the Z-axis drive mechanism 23 with respect to the Z-axis drive mechanism 23 extending in the vertical direction of the apparatus. The stage 4 can be moved in the vertical direction of the apparatus by the driving force of the Z-axis driving mechanism 23.

  A chamber heater 7 is provided inside the chamber 3 (processing space) as a processing space heating means for heating the inside of the chamber 3. In order to model a three-dimensional model by the hot melt lamination method (FDM), it is preferable to perform the modeling process in a state where the temperature in the chamber 3 is maintained at the target temperature. Therefore, before starting the modeling process, a pre-heat treatment is performed to raise the temperature in the chamber 3 to the target temperature in advance. The chamber heater 7 heats the chamber 3 to raise the temperature of the chamber 3 to the target temperature during the pre-heat treatment, and maintains the temperature in the chamber 3 at the target temperature during the modeling process. Therefore, the inside of the chamber 3 is heated. The operation of the chamber heater 7 is controlled by the control unit 100.

  Moreover, the chamber 3 is comprised with the heat insulating material, or is comprised with the member provided with the heat insulating material, and becomes the structure by which the heat | fever in the chamber 3 was suppressed from escaping outside. In particular, the X-axis drive mechanism 21, the Y-axis drive mechanism 22, and the Z-axis drive mechanism 23 are disposed outside the chamber 3. Therefore, the X-axis drive mechanism 21, the Y-axis drive mechanism 22, and the Z-axis drive mechanism 23 are not exposed to the high temperature in the chamber 3, and stable drive control is realized.

  In addition, an in-device cooling device 8 for cooling the space inside the three-dimensional object manufacturing device 1 outside the chamber 3, a nozzle cleaning unit 9 for cleaning the injection nozzle 11 of the heating head 13, and the like are provided. It has been.

Here, FIG. 2A to FIG. 2C show schematic views illustrating an example of a method for manufacturing a three-dimensional structure using the three-dimensional structure material of the present invention. FIG. 2A is a plan view illustrating an example of a three-dimensional modeled object modeled using the model material 20 and the support material 10. FIG. 2B is a cross-sectional view taken along line AA of the three-dimensional structure in FIG. 2A.
2A to 2C, the support portion 10 is stacked to support the handle portion because the handle portion in FIGS.
FIG. 2C is a schematic cross-sectional view illustrating an example of a process of removing the support material 10 from the three-dimensional structure illustrated in FIG. 2B. Since the support material 10 is made of a water-soluble thermoplastic resin, when the three-dimensional structure obtained in FIG. 2B is immersed in a container filled with cold water or warm water, only the support material 10 is dissolved and removed. Thus, a three-dimensional modeled object modeled with the model material 20 can be easily obtained.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Production Example 1)
-Preparation of plate-like inorganic particles A-
As a plate-like inorganic particle, 2% by mass of a silane coupling agent (KBE-1003, manufactured by Shin-Etsu Silicone Co., Ltd.) is added to mica (A-11, manufactured by Yamaguchi Mica Co., Ltd.), and a Henschel mixer (FM mixer, Japan). Coke Kogyo Co., Ltd.) produced a plate-like inorganic particle A by direct surface treatment under the conditions of a peripheral speed of rotating blades of 40 m / s, a mixing time of 10 minutes, and a treatment temperature of 25 ° C.

(Production Examples 2 to 13)
-Production of plate-like inorganic particles B to M-
In production example 1, plate-like inorganic particles B to M were produced in the same manner as in production example 1 except that the plate-like inorganic particles and processing conditions shown in Table 1 were changed.

<Long axis average particle size>
The long axis particle diameter of 20 particles was measured by cross-sectional SEM observation, and the average value was defined as the long axis average particle diameter. The major axis particle size means the longest axis length among the XYZ axis lengths of the particle shape.

<Aspect ratio>
The particle thickness of 20 particles was measured by cross-sectional SEM observation, and the average value was defined as the average particle thickness. The major axis average particle size was divided by the average particle thickness to calculate the aspect ratio.

* Mica (A-11, manufactured by Yamaguchi Mica Co., Ltd.)
* Mica ground product (A-11, manufactured by Yamaguchi Mica Co., Ltd.)
* Organic substituted montmorillonite (Kunifil-D36, manufactured by Kunimine Kogyo Co., Ltd.)
* Plate-like alumina (BMT-B, manufactured by Kawai Lime Industry Co., Ltd.)
* Spherical silica (FB-3SDC (3.3), manufactured by DENKA CORPORATION)
* Silane coupling agent (KBE-1003, manufactured by Shin-Etsu Silicone Co., Ltd.)
* Titanate coupling agent (TTS, manufactured by Ajinomoto Fine Techno Co., Ltd.)
* Aluminate coupling agent (AL-M, manufactured by Ajinomoto Fine Techno Co., Ltd.)

Example 1
-Production of thermoplastic resin composition-
As a thermoplastic resin, 100 parts by mass of acrylonitrile-butadiene-styrene copolymer resin (ABS) (Stylac 190, manufactured by Asahi Kasei Chemicals Corporation) and 5 parts by mass of plate-like inorganic particles A were converted into a twin-screw extruder (Xplore Instruments). Manufactured by MC 15), and melt kneaded under the conditions of a temperature of 240 ° C., a rotation speed of 100 rpm, and a feed amount of 1 kg / hr, to prepare a thermoplastic resin composition.

-Production of materials for 3D modeling-
Using the obtained thermoplastic resin composition, using a 3D filament material production extruder nozzle pro manufactured by Nippon Binary Co., Ltd., at a melting temperature of 230 ° C., a discharge speed of 0.5 m / min, and a draw ratio of 1 time, A filament-shaped three-dimensional modeling material having a diameter of 1.75 mm was produced.

-Production of 3D objects-
The obtained three-dimensional modeling material was subjected to the conditions of a nozzle temperature of 230 ° C., a bed temperature of 75 ° C., and a layer height of 0.20 mm using an FDM 3D printing device (XYZ Printing, Da Vinci 1.0 Pro). The three-dimensional modeled object shown in FIG. 3 was modeled on a scale of 100 mm × 60 mm.

  About the obtained three-dimensional model | molding material and three-dimensional model | molding thing, various characteristics were evaluated as follows. The results are shown in Table 3.

<Modeling stability>
Using a three-dimensional modeling material, a three-dimensional model was modeled at a modeling speed of 60 mm / s and 100 mm / s, whether or not modeling was possible, and modeling stability was evaluated according to the following criteria.
[Evaluation criteria]
○: Successful modeling for both modeling speed 60 mm / s and 100 mm / s Δ: Successful modeling for modeling speed 60 mm / s, failed modeling for 100 mm / s ×: Modeling failed for both modeling speed 60 mm / s and 100 mm / s

<Warpage amount>
The produced three-dimensional model was placed on a flat table, the right side of the three-dimensional model was pressed, and the gap (the amount of warpage) between the left side of the model and the flat table was measured using a gauge and evaluated according to the following criteria.
[Evaluation criteria]
◎: Warpage amount is 0.05 mm or less ○: Warpage amount is more than 0.05 mm and 0.1 mm or less △: Warpage amount is more than 0.1 mm and 0.2 mm or less ×: Warpage amount is more than 0.2 mm and less than 0.3 mm

<Surface polishing>
In order to make the surface of the three-dimensional modeled object flat, it was polished using a # 1200 sandpaper and evaluated according to the following criteria.
[Evaluation criteria]
◎: The surface of the molded object could be polished without problems. ○: The surface of the molded object could be polished without problems, but streaks remained on the surface. △: When the surface of the molded object was polished, irregularities were formed on the surface. Could not be polished

<Dimensional accuracy>
The detailed dimensions of the produced three-dimensional model were measured with calipers, the difference from the 3D data of the model was determined, and evaluated according to the following criteria.
[Evaluation criteria]
A: The difference between the measured dimension and the 3D data is within ± 0.5%. A: The difference between the measured dimension and the 3D data is more than ± 0.5% and within ± 1.0%. Δ: The difference between the measured dimension and the 3D data is more than ± 1.0% and within ± 2.0%. X: The difference between the measured dimension and the 3D data is larger than ± 2.0%.

<Comprehensive evaluation>
Based on the evaluation results of the three-dimensional modeling material and the three-dimensional modeled object, comprehensive evaluation was performed.
[Evaluation criteria]
◎: Evaluation result of each item, ◎ is 3 or more, no evaluation item of △, × ○: Evaluation result of each item, ◎ is 1-2, there is no evaluation item of △, × △: For each item In the evaluation result, x is 1 or less ×: In the evaluation result of each item, x is 2 or more

(Examples 2 to 15 and Comparative Examples 1 to 7)
In Example 1, except that the thermoplastic resin, the plate-like inorganic particles, and the organometallic compound shown in Table 2 were changed, a material for three-dimensional modeling and a three-dimensional modeled object were produced in the same manner as in Example 1, and the same Thus, various characteristics were evaluated. The results are shown in Table 3.

* ABS: Acrylonitrile-butadiene-styrene copolymer resin (Stylac 190, manufactured by Asahi Kasei Chemicals Corporation)
* PC: Polycarbonate resin (Novalex, manufactured by Mitsubishi Engineering Plastics)
* PA12: Polyamide 12 resin (UBESTA, Ube Industries, Ltd.)
* Magnesium stearate as an organometallic compound (SM-P, manufactured by Sakai Chemical Industry Co., Ltd.)

Aspects of the present invention are as follows, for example.
<1> a thermoplastic resin;
It is a three-dimensional modeling material characterized by containing plate-like inorganic particles having an organometallic oxide group on the surface.
<2> The material for three-dimensional modeling according to <1>, wherein the metal in the organometallic oxide group is any one of Si, Ti, and Al.
<3> The three-dimensional structure forming material according to <2>, wherein the organometallic oxide group is any one of alkoxysilane, alkoxytitanium, and alkoxyaluminum.
<4> The material according to any one of <1> to <3>, wherein the plate-like inorganic particles are at least one selected from metal oxides, inorganic layered silicates, and organic substitutes of swellable clay minerals. 3D modeling material.
<5> The three-dimensional modeling material according to <4>, wherein the metal oxide is alumina.
<6> The three-dimensional modeling material according to <4>, wherein the inorganic layered silicate is mica.
<7> The three-dimensional modeling material according to <4>, wherein the organic substitute of the swellable clay mineral is an organic substitute of montmorillonite.
<8> The material for three-dimensional modeling according to any one of <1> to <7>, wherein the content of the plate-like inorganic particles is 1% by mass or more and 10% by mass or less.
<9> The three-dimensional modeling according to any one of <1> to <8>, wherein the long axis average particle diameter of the plate-like inorganic particles is 1 μm or more and 3 μm or less, and the aspect ratio is 10 or more and 1,000 or less. Material.
<10> The three-dimensional material according to any one of <1> to <9>, wherein the thermoplastic resin includes an acrylonitrile-butadiene-styrene copolymer resin (ABS).
<11> The material for three-dimensional modeling according to any one of <1> to <10>, further including an organometallic compound.
<12> The three-dimensional material according to <11>, wherein the organometallic compound is a metal soap.
<13> The three-dimensional modeling material according to <12>, wherein the metal soap is magnesium stearate.
<14> The material for three-dimensional modeling according to any one of <1> to <13>, wherein the material is any one of a filament shape, a pellet shape, and a particle shape.
<15> The material for three-dimensional modeling according to <14>, wherein the filament has a diameter of 1 mm to 5 mm.
<16> The three-dimensional structure forming material according to any one of <1> to <15>, which is at least one of a three-dimensional structure forming material and a support forming material.
<17> A method for producing a three-dimensional structure, comprising producing a three-dimensional structure using the three-dimensional structure material according to any one of <1> to <16>.
<18> The material for three-dimensional modeling according to any one of <1> to <16>,
It has a heating head which melts and discharges the above-mentioned three-dimensional modeling material.

  According to the three-dimensional structure manufacturing material according to any one of <1> to <16>, the three-dimensional structure manufacturing method according to <17>, and the three-dimensional structure manufacturing apparatus according to <18>, The above problems can be solved and the object of the present invention can be achieved.

Japanese Patent No. 5751388 JP 2016-28887 A

DESCRIPTION OF SYMBOLS 1 3D modeling manufacturing apparatus 10 Support material 13 Heating head 20 Model material

Claims (10)

A thermoplastic resin;
A three-dimensional modeling material comprising: plate-like inorganic particles having an organometallic oxide group on the surface thereof.   The material for three-dimensional modeling according to claim 1, wherein the metal in the organometallic oxide group is any one of Si, Ti, and Al.   The material for three-dimensional modeling according to claim 2, wherein the organometallic oxide group is any one of alkoxysilane, alkoxytitanium, and alkoxyaluminum.   The three-dimensional modeling material according to any one of claims 1 to 3, wherein the plate-like inorganic particles are at least one selected from metal oxides, inorganic layered silicates, and organic substitutes of swellable clay minerals.   5. The material for three-dimensional modeling according to claim 1, wherein the content of the plate-like inorganic particles is 1% by mass or more and 10% by mass or less.   The three-dimensional modeling material according to any one of claims 1 to 5, wherein the plate-like inorganic particles have a major axis average particle size of 1 µm to 3 µm and an aspect ratio of 10 to 1,000.   The material for three-dimensional modeling according to any one of claims 1 to 6, further comprising an organometallic compound.   The material for three-dimensional modeling according to any one of claims 1 to 7, wherein the material is one of a filament shape, a pellet shape, and a particle shape.   A method for producing a three-dimensional object, comprising producing a three-dimensional object using the three-dimensional object material according to any one of claims 1 to 8. The material for three-dimensional modeling according to any one of claims 1 to 8,
A three-dimensional object manufacturing apparatus, comprising: a heating head that melts and discharges the three-dimensional object material.