JP3222767U - Modeling material - Google Patents

Abstract

A modeling material capable of obtaining a modeled object having a new variation in a modeling material for a 3D printer is provided. SOLUTION: A linear body having a diameter of 0.5 to 10 mm, the linear body is a modeling material 1 for obtaining a desired molded object by applying to an additional manufacturing apparatus, and the linear body is Constructed of a thermoplastic synthetic resin, the modeling material 1 has a structural color. Or it is a linear body of diameter 0.5-10mm, Comprising: This linear body is the modeling material 1 for obtaining a desired molded article by applying to an addition manufacturing apparatus, and this linear body is thermoplastic. It is composed of a synthetic resin, and the thermoplastic synthetic resin includes a structural color developing colorant. [Selection] Figure 1

Description

  The present invention relates to a modeling material for use in an additional manufacturing apparatus (three-dimensional printer).

  The resin molded body is molded by various methods such as injection molding and extrusion molding, and is widely used in the fields of daily necessities and industrial fields. As a method for obtaining a small amount of various types of molded products, a molding method using a three-dimensional modeling machine represented by a three-dimensional printer (3D printer) has been attracting attention.

  3D printer methods include hot melt lamination (FDM), stereolithography (SLA), and powder sintering lamination (SLS), and technological development is underway for each. FDM modeling equipment is widely used for personal use, and linear bodies made from thermoplastic synthetic resins such as ABS resin (acrylonitrile-butadiene-styrene copolymer) and polylactic acid resin are known as modeling materials. It has been.

  For example, Patent Document 1 discloses that an average diameter of 0.069 to 0.074 inches (about 1.75 to 1.90 mm) and a length of 20 feet (about 6) as materials for enabling high-precision modeling. 1 m) or more and a modeling material having a standard deviation in diameter of 0.0004 inches (0.01 mm) or less is disclosed.

JP 2005-523391 A

  A modeling material for a 3D printer capable of obtaining a small amount and a variety of molded products is expected to have various variations such as various functions and textures. This invention makes it a subject to propose the modeling material which can obtain the modeling object which has a new variation in the modeling material for 3D printers.

  The present invention is a linear body having a diameter of 0.5 to 10 mm, and the linear body is a modeling material for obtaining a desired model by applying it to an additional manufacturing apparatus. The gist of the modeling material is made of a plastic synthetic resin, and the modeling material has a structural color.

  Further, the present invention is a linear body having a diameter of 0.5 to 10 mm, and the linear body is a modeling material for obtaining a desired modeling object by applying to an additional manufacturing apparatus, and the linear body Is made of a thermoplastic synthetic resin, and the gist is a modeling material characterized in that the thermoplastic synthetic resin contains a structural color developing colorant.

  The modeling material of the present invention is made of a thermoplastic synthetic resin and is a linear body having a diameter of 0.5 to 10 mm. The linear body is a continuous linear object of several m to several hundreds m, and is wound into a reel to be attached to a 3D printer to obtain a molded body (modeled object) having a desired shape. A preferable diameter of the modeling material is 1 mm or more, and in particular, a modeling material having a diameter of 1.75 mm is preferable because it can be applied to a 3D printer by a commercially available hot melt lamination method. The linear body may be cut into a predetermined length of about 3 mm to 1000 mm as necessary.

  The modeling material of the present invention has a structural color. In order for a modeling material to have a structural color, the method of including a structural color expression color material in a thermoplastic synthetic resin is more effective. Structural color means that a unique color such as pearl, iridescent, morpho butterfly wing, opal is expressed by thin film interference, multilayer interference, diffraction, light scattering, Mie scattering, refraction, etc. The expression colorant is a colorant that expresses the unique color described above. The structural color developing colorant is particularly preferably a colorant exhibiting a highly anisotropic structural color such as a play color effect (color travel effect). Examples of the structural color-expressing coloring material include composite pigments that are made of powder or flakes such as aluminum and mica and coated with silica, titanium oxide, metal fine particles, and the like. Such structural color developing color materials may be used alone or in combination of two or more.

  The particle diameter of the structural color developing coloring material is not limited as long as it can be satisfactorily contained in the thermoplastic synthetic resin and can be melt-spun, but the maximum diameter is preferably 100 μm or less. By setting the maximum diameter to 100 μm or less, clogging of the nozzle pack is less likely to occur during melt spinning, it is possible to perform melt spinning well, and troubles such as nozzle clogging occur when modeling with a 3D printer. It becomes difficult. For these reasons, the maximum diameter is more preferably 50 μm or less. The lower limit of the particle size is preferably 0.01 μm from the viewpoint of handleability. In addition, processing for adjusting kneadability, dispersibility, and heat resistance with the thermoplastic synthetic resin, surface treatment (for example, coating, microencapsulation, plasma treatment, masterbatch formation) and the like may be performed.

  The ratio of the structural color developing color material to be included in the thermoplastic synthetic resin may be appropriately designed according to the specific gravity and compatibility of the material, the kneading method for inclusion, and the particle size of the structural color developing color material. 0.1-30 mass parts is good for a structural color expression coloring material with respect to 100 mass parts. When the amount of the structural color developing color material is less than 0.1 parts by mass, it is difficult to obtain sufficient structural color developing properties. In addition, by setting the amount of the structural color developing coloring material to 30 parts by mass or less, the linear body is not easily broken at the time of modeling, and the obtained molded object does not become brittle, and has a strength that is not easily destroyed in normal use. Can be maintained.

  In addition to having a structural color, the modeling material of the present invention preferably has chromic properties. The chromic property is a property that changes color when heat, light, electricity, solvation, pressure, etc. are applied.For example, when it has structural color and thermochromic property, it is below the discoloration temperature and above the discoloration temperature of the thermochromic color material. The color and gloss of the external appearance can be changed, and the gloss and hue depth of the structural color are added to the color to give a high design. In the case of a chromic color material that responds to a stimulus other than heat, the appearance can be changed at any time, and the design can be further enhanced.

  The chromic property can be achieved by including a chromic color material in the thermoplastic synthetic resin. The chromic colorant can be a thermochromic colorant (for example, a halogeno complex, a dinitrodiammine copper (II) complex, an ethylenediamine nickel (II) complex, a salicylaldehyde complex, a cholesteric liquid crystal of a polypeptide, a leuco dye). ), Photochromic color materials (eg, azobenzene, spiropyran, diarylethene) if light, electrochromic color materials (eg, viologen compounds, tungsten oxide) if electricity, and solvatochromic color materials (eg, solvates) , 2,6-diphenyl-4- (2,4,6-triphenylpyridinio) phenolate), and pressure may be a piezochromic coloring material (for example, a metal-dione dioximate complex). These chromic color materials may be used alone or in combination of two or more.

  The particle size of the chromic color material may be contained in the thermoplastic synthetic resin as long as it can be melt-spun, but for the same reason as the structural color expression color material, the maximum diameter is preferably 100 μm or less, More preferably, it is preferably 50 μm or less, and the lower limit is preferably 0.01 μm in view of handling. In addition, processing for adjusting kneadability, dispersibility, and heat resistance with the thermoplastic synthetic resin, surface treatment (for example, coating, microencapsulation, plasma treatment, masterbatch formation) and the like may be performed.

  The ratio of the chromic color material to be included in the thermoplastic synthetic resin may be appropriately designed depending on the specific gravity and compatibility of the material, the kneading method for inclusion, and the particle size of the chromic color material. On the other hand, the structural color developing colorant is preferably 0.01 to 10 parts by mass.

  Examples of the thermoplastic synthetic resin constituting the modeling material of the present invention include polyester resins, polyamide resins, polyolefin resins, polycarbonate resins, acrylic resins, vinyl resins, and thermoplastic elastomers. Among these, polyester resins can be preferably used because of easy adjustment of mechanical properties and high versatility.

  Among the polyester-based resins, polylactic acid is preferable because warpage is unlikely to occur, and poly-L lactic acid having a low D-form content is more preferable because it is difficult to be yellowish. In order to make it less yellowish, the D-form content is preferably less than 1.5 mol%.

  Further, a polyester copolymer having a melting point of about 130 to 200 ° C. can be preferably used. At the time of modeling, the 3D printer needs to be set to a temperature equal to or higher than the melting point of the thermoplastic synthetic resin. By setting the upper limit of the melting point of the thermoplastic synthetic resin constituting the modeling material to 200 ° C. or lower, the set temperature of the 3D printer Is preferable because it is not necessary to set the temperature to a very high temperature. As the polyester copolymer having a melting point of about 130 to 200 ° C., a polyester copolymer described in Japanese Patent Application No. 2018-527633 proposed by the present applicant can be preferably used. This polyester copolymer is a polyester copolymer containing terephthalic acid as an acid component and ethylene glycol and 1,4-butanediol as a diol component, preferably having a melting point of 130 to 200 ° C., and having a glass transition The temperature is 50 ° C. or lower, and the crystallization temperature is 120 ° C. or lower. For this reason, when the shaped object to be obtained is heated to the glass transition temperature or higher, the shape can be easily changed.

  Therefore, this polyester copolymer is used as the thermoplastic synthetic resin constituting the modeling material, and the polyester copolymer is incorporated with a structural color developing colorant and a thermochromic colorant, and the shape of the polyester copolymer If the changeable temperature and the color change temperature of the thermochromic color material are aligned, the shape and rigidity change in addition to the color and gloss change, and the design is greatly improved. Therefore, if this polyester copolymer is used as the thermoplastic synthetic resin that constitutes the modeling material, the resulting modeled product can be heated and softened if it contains a structural color developing color material and a thermochromic color material. When the shape is changed, the color tone and gloss change due to the change in the curvature of the shape and the orientation of the end face. Therefore, an appearance change that cannot be obtained by simple shape change occurs, and the design is further improved.

  The polyester copolymer may contain other monomer components as long as the object of the present invention is not impaired. For example, diethylene glycol, 1,3-propanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane Examples include dimethanol, cyclohexane glycol, succinic acid, adipic acid, azelaic acid, sebacic acid, isophthalic acid, and ε-caprolactone. By using these components as appropriate, properties such as crystallinity, rigidity, and temperature characteristics can be adjusted. Is possible.

  The thermoplastic synthetic resin constituting the modeling material may be a polymer blend composed of two or more synthetic resins. Further, in the thermoplastic synthetic resin, in addition to the structural color expression color material and chromic color material, dyes, pigments, fluorescent pigments, phosphorescent pigments, compatibilizers, spreading agents, within a range that does not impair the purpose of the present invention. Lubricants, fillers, antioxidants, light absorbers, stabilizers, flame retardants, pH adjusters, antibacterial agents, preservatives, preservatives, fragrances, plasticizers, viscosity modifiers, clearing agents, antistatic agents, crystals Additives such as nucleating agents may be included. However, it is preferable that the thermoplastic synthetic resin has high transparency in order to develop the color of the structural color developing color material more effectively and strongly. Therefore, it is preferable to determine the polymer blend and additive formulation so that transparency and color development according to the purpose can be obtained. For example, if the thermoplastic synthetic resin used for the modeling material is a hard and brittle resin such as polylactic acid, and a relatively large amount of coloring material is added, the resulting molding material is bent during manufacturing and handling. When subjected to a load such as, it is easy to break or break, so plasticizers, softeners, low-rigidity, high-toughness polymers, thermoplastic elastomers are used as long as the intended performance of the present invention is not impaired. It is preferable to add flexural resistance and impact resistance, etc. to add transparency, etc.If the reflection at the interface of the blended material impairs transparency, the compatibility of the interface is increased with a compatibilizer to improve transparency. You may let them.

  The linear body constituting the modeling material may be in a single-phase form or a multi-phase form in which a plurality of polymers are combined, such as a core-sheath type or a side-by-side type. As a method for obtaining a molding material in a multi-phase form, a method of melt extrusion using a composite nozzle, a method of forming a multi-phase by coating, and a method in which a plurality of linear bodies are integrated by methods such as pressure bonding, adhesion, and welding. Methods.

  When the modeling material is in a multi-phase form, the thermoplastic synthetic resin containing the structural color developing color material may be arranged in at least any one of a plurality of phases, but the volume of the phase composed of the structural color developing color material If the total ratio is 30% or more, it is preferable because the function can be sufficiently exerted after addition production, and more preferably 50% or more.

  Alternatively, a structural color developing color material may be carried on the outermost layer of a single-phase or multi-phase linear body to form a modeling material. Examples of the supporting method include thermal bonding, chemical bonding, chemical bonding, pressure bonding, close contact, dipping, exhaust dust, and the like.

  The modeling material of the present invention can be obtained as a continuous linear body by melting a raw material mainly composed of a thermoplastic synthetic resin and extruding it from a spinning nozzle. For example, a raw material is spun by a melt spinning method, and then stretched to crystallize a thermoplastic synthetic resin to obtain a linear body, or after spinning, a linear body is obtained in an unstretched state. You may crystallize the linear body extract | collected by non-stretching by post-processing heat processing.

  While it is expected to have various variations such as various functions and textures as a modeling material by a 3D printer, according to the modeling material that exhibits various structural colors in the present invention, a modeling object having a new variation Can be obtained. Therefore, the design property when using a modeled object obtained from the modeling material of the present invention for interiors, decorations, art works, etc. is increased, resulting in high added value.

It is a schematic perspective view which shows the modeling material (1) of the linear body of this invention. The modeling material (1) is continuous and is wound around the reel (2).

  The present invention will be specifically described based on examples. In the following Examples and Comparative Examples, in the modeling test using a 3D printer, a model was created using a 3D printer “DavinciPro” manufactured by XYZprinting.

Example 1
For 100 parts by mass of polyester copolymer chip (copolymer polyester consisting of 50 mol% terephthalic acid, 25 mol% ethylene glycol, 25 mol% 1,4-butanediol, specific gravity 1.38, melting point 180 ° C.) Resin (trade name “Eritel UE-3210” manufactured by Unitika Ltd.) 10 parts by mass, spreading agent (trade name “Moresco White P-350P” manufactured by Matsumura Sekiyu Co., Ltd.) 0.2 parts by mass, expression color of structural color A material (resin composition) added with 1 part by mass of a material (trade name “POLYCOOL METM-112012 Pearl” manufactured by Polycol Kogyo Co., Ltd.) was melt-spun at an spinning temperature of 200 ° C. with an extruder-type spinning machine. A strand-like product was obtained by stretching. Next, the strand-like material is introduced into a hot air dryer, subjected to heat treatment at 75 ° C. for 60 minutes in an unloaded state, air-cooled, and formed into a continuous linear body having a circular cross section having a diameter of 1.75 mm. Obtained material. The modeling material was matt white as a whole due to the crystallization of the base resin, and a slight pearly luster was seen. When the modeling material obtained was subjected to a modeling test (modeling temperature 200 ° C.) using a 3D printer, a white modeled object having a desired shape and a desired shape was obtained. In the modeled object, the pearl-like luster was strongly observed because the base resin was amorphized and cleared by remelting.

Example 2
In Example 1, the same raw material was used as the structural color expression color material except that the trade name “Chromashine MBL-20X” manufactured by Toyo Aluminum Co., Ltd. was used, and the spinning temperature was 200 ° C. with an extruder type spinning machine. Was subjected to melt spinning and stretched in a warm bath to obtain a modeling material which is a continuous linear body having a circular cross section having a diameter of 1.75 mm. The modeling material was dark blue as a whole, and a play-coloring effect with different blue shades depending on the viewing angle was observed. When the modeling material obtained was subjected to a modeling test (modeling temperature 200 ° C.) using a 3D printer, a dark blue modeled object having a desired shape and a desired shape was obtained. It was.

Example 3
Using the same raw material as in Example 2, melt spinning was performed to obtain a dark blue strand that was unstretched and clear. Next, the strand material is introduced into a hot air dryer, subjected to heat treatment at 75 ° C. for 60 minutes in an unloaded state, air-cooled, and a modeling material that is a continuous linear body having a circular cross section with a diameter of 1.75 mm. Got. The modeling material was matte blue as a whole due to crystallization of the base resin, and almost no play effect was observed. When the modeling material obtained was subjected to a modeling test (modeling temperature 200 ° C.) with a 3D printer, a clear dark blue modeled object having a desired shape and a desired shape was obtained. In the modeled object, the base resin was amorphized and cleared by remelting, and a play-color effect was seen.

Example 4
In Example 1, the resin composition used in Example 1 was further mixed with a chromic colorant (trade name “chromicolor PEConc BW grade manufactured by Matsui Dye Chemical Co., Ltd.) with respect to 100 parts by mass of the polyester-based copolymer chip. # 37 F-0 ") A molding material was obtained in the same manner as in Example 1 except that 1 part by mass was added.

  When the obtained modeling material was observed in a 20 ° C. environment, it was a matte pink color as a whole, and a slight pearly luster was observed. When this was placed in a 50 ° C. environment, it changed to a matte white with a little pearly luster. Moreover, when it returned to 20 degreeC environment, it returned to the original mat pink color gradually.

  When the modeling material obtained was subjected to a modeling test (modeling temperature 200 ° C.) with a 3D printer, a pink modeled object having a desired shape and a desired shape was obtained. In the modeled object, the pearl-like luster was strongly observed because the base resin was amorphized and cleared by remelting. Further, when the obtained shaped article was placed in a 50 ° C. environment, the color changed to white having a pearly luster. Moreover, when it returned to 20 degreeC environment, it returned to the original pink color gradually.

Comparative Example 1
Using only a polylactic acid resin (specific gravity 1.24, melting point 165 ° C.), in the same manner as in Example 1, melt spinning with an extruder-type spinning machine, and without stretching, a colorless molding having a diameter of 1.75 mm Obtained material. The obtained modeling material was subjected to a modeling test with a 3D printer in the same manner as in Example 1. As a result, although it could be modeled without any problem, it had the same appearance as a general commercially available PLA filament, and no particular design was found. It was.

1: Modeling material 2: Reel

Claims (7)

  A linear body having a diameter of 0.5 to 10 mm, and the linear body is a modeling material for obtaining a desired model by applying it to an addition manufacturing apparatus, and the linear body is made of a thermoplastic synthetic resin. A modeling material, characterized in that the modeling material has a structural color.   The modeling material according to claim 1 has chromic properties in addition to having a structural color.   A linear body having a diameter of 0.5 to 10 mm, and the linear body is a modeling material for obtaining a desired model by applying it to an addition manufacturing apparatus, and the linear body is made of a thermoplastic synthetic resin. A molding material comprising a thermoplastic synthetic resin containing a structural color-expressing colorant.   The molding material according to claim 3, wherein the thermoplastic synthetic resin includes a structural color developing colorant and a chromic colorant.   The molding material according to any one of claims 1 to 4, wherein the thermoplastic synthetic resin is a polyester-based resin.   The polyester resin is a polyester resin mainly comprising a polyester copolymer containing terephthalic acid as an acid component and ethylene glycol and 1,4-butanediol as a diol component. Modeling material. A modeled object obtained by using the modeling material according to any one of claims 1 to 6, wherein the modeled object has a structural color.