JP6513605B2 - Filament for 3D printing - Google Patents

Description

  The present invention is for three-dimensional printing which can display different colors, patterns and information at the time of ultraviolet irradiation by adding a light-emitting substance which is usually colorless and transparent and visible at the time of ultraviolet irradiation to a filament for conventional three-dimensional printing. It relates to a filament.

Three-dimensional (3D) printing has gained much attention in recent years. Several different methods exist, and articles, prototypes and working constructs can be prepared.
As a main method, an optical modeling method, powder sintered lamination molding, a hot melt lamination method, a gypsum 3D printer, an inkjet system, etc. may be mentioned. Among them, the hot melt lamination method is most commonly used at present.

  The hot melt lamination method is a method of melting a filament of a thermoplastic resin at a high temperature and laminating it to form a three-dimensional shape. The resin spool is extruded with a pulley in the shaping head, and the resin is melted with a heater at the tip, and lamination is performed with the extruded resin.

On the other hand, the application of three-dimensional printing has been spreading rapidly in recent years, and has spread in a wide range of fields such as architecture, medical care, education, aerospace, and advanced research centering on manufacturing industries.
In the manufacturing field, as prototypes and mockups for “design study” and “functional verification” of products and parts etc. In the construction field as “architectural models” for competitions and presentations, in the medical field, computed tomography and nuclear magnetic resonance imaging It is used as a "preoperative examination model" based on such data.
In the field of education, "tool for manufacturing education", in the aerospace field, the production of functional parts of jet engines and rocket engines, in the advanced research field, the creation of "test parts", "jigs" etc. Used in applications.
In addition, with the prosperity of low price 3D printer market that can be purchased for 100,000 yen or less, the use for personal use such as hobby use and DIY is also increasing.

As the applications increase, various colors are required for three-dimensional structures created using three-dimensional printing. It can be said that ordinary paints which can be recognized in daytime and bright rooms as well as luminescent substances which can exhibit decorative effects even in the dark.
However, few filaments have been developed focusing on colors using fluorescent paint of three-dimensional printing.

For example, as a filament for three-dimensional printing that essentially includes a luminescent material, Patent Document 1 can be mentioned.
Patent Document 1 describes a method for producing a three-dimensional structure that can efficiently produce a three-dimensional structure including information that can be read when necessary but can not be identified in a normal state. ing. More specifically, it contains a paint (titanium oxide, carbon black, etc.) visible to the ink for forming the substantial part as a color that can be usually recognized, and can be seen by irradiating a predetermined radiation (X-ray, ultraviolet light, visible light, etc.) The latent portion forming ink is characterized in that it contains a fluorescent material.
However, what is mentioned as a fluorescent material in the invention described in Patent Document 1 is C.I. I. Direct yellow or C.I. I. Acid red and the like are commonly used fluorescent paints, and when dissolved in a resin, they exhibit opalescent white color which lightens the color of each fluorescent paint under normal light. Therefore, it is possible to know what color of fluorescent paint is used even under normal light, so for example an event stage or a karaoke box illuminated by a black light does not have a significant impact. Have.
Furthermore, when a visible pigment that can be viewed under normal light is also used at the same time, if the fluorescent paint exhibits a milky white color under normal light, the color of the visible pigment and the color of the fluorescent paint mix under normal light. Have the problem of being undesirable.

  In addition, although the patent documents 2 and 3 are mentioned as a composition for three-dimensional printing described that it contains that a luminescent material is described, The fluorescent paint as a coloring agent candidate similar to the paint which can be visually recognized also in the daytime However, there is no specific description of what kind of light-emitting substance to use.

  Therefore, when viewed in the daytime or under fluorescent light, it can not be viewed at all, and the color effect of the three-dimensional object can be imparted together with the desired color on an event stage or a karaoke box etc. There is a demand for three-dimensional objects that are not available in the past.

JP, 2015-174426, A Japanese Patent Publication No. 2016-501136 gazette JP, 2016-16568, A

  The present invention is a third-order display capable of clearly displaying different patterns and information between normal time and ultraviolet light irradiation by adding a light-emitting material which is usually colorless and transparent and can be recognized at the time of ultraviolet light irradiation to a conventional filament for three-dimensional printing. It is an object to provide a filament for original printing.

The invention according to claim 1 is an acrylonitrile butadiene styrene copolymer, polylactic acid, polypropylene, polystyrene, high impact polystyrene, styrene butadiene, thermoplastic polyester elastomer, thermoplastic polyurethane, polycarbonate, polymethyl methacrylate resin, soft acrylic, And at least one resin selected from polyethylene terephthalate, europium compounds emitting red light under ultraviolet irradiation, naphthalene compounds emitting blue light, and terbium compounds emitting green light , A filament for three-dimensional printing comprising a luminescent material which is colorless and transparent under non-ultraviolet radiation , and is characterized in that it emits light when irradiated with ultraviolet radiation ; about .

  The invention according to claim 2 relates to a filament for three-dimensional printing according to claim 1, characterized in that the europium-based compound is a compound represented by any one of the following formulas 1 to 4. .

  The invention according to claim 3 relates to the filament for three-dimensional printing according to claim 1 or 2, wherein the naphthalene compound is a compound represented by the following chemical formula 5.

  The invention according to claim 4 is that for the three-dimensional printing according to any one of claims 1 to 3, characterized in that the terbium-based compound is a compound represented by the following formula 6 or 7 On the filament of

In the invention according to claim 5, the resin is at least one resin selected from the group consisting of polystyrene, polycarbonate, polymethyl methacrylate resin, and polyethylene terephthalate, and the filament is colorless and transparent under non-ultraviolet irradiation. It relates to a filament for three-dimensional printing according to any one of claims 1 to 4, characterized in that

In the present invention, the resin is selected from acrylonitrile butadiene styrene copolymer, polylactic acid, polypropylene, polystyrene, high impact polystyrene, styrene butadiene, thermoplastic polyester elastomer, thermoplastic polyurethane, polycarbonate, polymethyl methacrylate resin, soft acrylic it characterized in that one or more selected.

Since the filament for three-dimensional printing according to claim 1 emits light when irradiated with ultraviolet light, it emits strong light at an event stage using a black light, a blue LED, a purple LED or the like, a karaoke box, etc. Can have a decorative effect.
The present invention can be easily manufactured by adding a luminescent material to a conventional filament.
In addition, since the light-emitting substance contained in the filament emits red, blue, and green under ultraviolet irradiation, the luminous color of the three-dimensional structure at the time of ultraviolet irradiation can be various colors by including one or more of them. It becomes possible. For example, a combination of a light emitting substance that emits red light and a light emitting substance that emits green light produces a yellow light emission color, and a combination of a light emitting substance that emits red light and a light emitting substance that emits blue light produces a purple light emission color. The combination of the luminescent material and the luminescent material emitting green light produces a white luminescent color.

  The filament for three-dimensional printing containing the luminescent material according to claims 2 to 4 is excellent in the luminescent ability and does not lose the luminescent effect for a long time than the conventional luminescent material.

  The filament for three-dimensional printing according to claim 5 is colorless and transparent unless irradiated with ultraviolet light, so that the light-emitting substance should preferably be used without disturbing the color tone of the three-dimensional structure at the time of non-ultraviolet irradiation. it can.

In the filament for three-dimensional printing according to the present invention , said resin is acrylonitrile butadiene styrene copolymer (ABS), polylactic acid, polypropylene, polystyrene, high impact polystyrene, styrene butadiene, thermoplastic polyester elastomer or thermoplastic polyurethane It can be suitably used for three-dimensional printing by using at least one selected from thermoplastic elastomers such as, polycarbonate, polymethyl methacrylate resin (PMMA) and soft acrylic.

Hereinafter, the filament for three-dimensional printing of the present invention will be described.
In the filament of the present invention, at least one light emitting substance selected from a europium-based compound emitting red light, a naphthalene-based compound emitting blue light, and a terbium-based compound emitting green light is dissolved in a thermoplastic resin It is a filament for three-dimensional printing.

First, the luminescent material is described.
The europium-based compound according to the present invention is a europium complex. Preferably, tris (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato-O, O'-) bis (triphenylphosphine oxide-O-) europium described above is used. 2), tris (4,4,4-trifluoro-1- (2-thienyl) -1,3-butanedionato-O, O'-) bis (triphenylphosphine oxide-O-) europium), 3 (tris (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato-O, O'-) bis (trioctylphosphine oxide-O-) europium) or 4 (tris A compound represented by (4,4,4-trifluoro-1- (2-thienyl) -1,3-butanedionato-O, O '-) bis (trioctylphosphine oxide-O-) europium) can be mentioned.
The compounds represented by the formula 1 and the compound 2 are solid at normal temperature, and the compounds represented by the formula 3 and the compound 4 are liquid at normal temperature.
Therefore, since the compounds represented by the above-mentioned 3 and 4 which are liquid at normal temperature can be easily and uniformly mixed with the resin, in the filament of the present invention, the compounds represented by 3 and 4 are used Is more preferred.

  The naphthalene compound according to the present invention is a compound containing naphthalene. Preferably, a compound represented by the above-mentioned chemical formula 5 (1,4-bis (2-benzoxazolyl) naphthalene) is mentioned.

  The terbium-based compound according to the present invention is a terbium complex. Preferably, the above-mentioned compound 6 (tris (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato-O, O '-) bis (triphenylphosphine oxide-O-) terbium And a compound represented by the formula 7 ([[hexadecakis (hexyl salicylate) octahydroxyl] dioxononatebium triethylamine salt).

  The light-emitting substances represented by the above-mentioned chemical formulas 1 to 7 are organic molecules which absorb light energy efficiently and can utilize light emission energy without waste. These luminescent materials have strong characteristics such as maintaining strong luminescence even when left standing at a high temperature of 200 ° C. for several hours. Therefore, the present invention including the luminescent materials is used even when it is hot in summer or under high temperatures. The luminous effect of the three-dimensional structure manufactured by

With regard to the emission color of the light-emitting substance according to the present invention, the europium-based compound emits light with a peak wavelength of 613 nm and emits red light under ultraviolet irradiation, and the naphthalene-based compound emits light with a peak wavelength of about 460 nm The terbium-based compound emits blue light and emits light with a peak wavelength of 542 nm to emit green light.
Therefore, it becomes possible to create an arbitrary color tone and emit light under ultraviolet irradiation by selecting the light-emitting substances emitting red, blue and green emitting these specific wavelengths in an arbitrary ratio.
For example, a combination of a light emitting substance that emits red light and a light emitting substance that emits green light produces a yellow light emission color, and a combination of a light emitting substance that emits red light and a light emitting substance that emits blue light produces a purple light emission color. The combination of the luminescent material and the luminescent material emitting green light produces a white luminescent color.

  The light emitting material has the property of becoming colorless and transparent when dispersed in a resin. Therefore, the color tone of the three-dimensional structure at the time of non-ultraviolet irradiation can be suitably used without the light-emitting substance disturbing it. For example, even when it is combined with a visible pigment, it can coexist without disturbing the color of the visible pigment under natural light or fluorescent light.

Furthermore, by using the above-mentioned light emitting material, even if there is a missing portion in the completed three-dimensional structure, it is possible to clearly grasp the portion by irradiating the ultraviolet light.
That is, by adding the light emitting substance to the resin, it is possible to create a three-dimensional structure excellent in dimensional stability.

  The content of the luminescent material according to the present invention is not particularly limited, but preferably 0.01 to 5% by weight based on the total amount of the filament. The reason is that if the content is less than 0.01% by weight, a sufficient light emitting effect can be provided, and if 5% by weight or more is added, no further light emitting effect can be obtained, which is economically unpreferable.

  The thermoplastic resin contained in the filament of the present invention is not particularly limited as long as it is generally used as a resin for three-dimensional printing. For example, any one or more of ABS resin, polylactic acid and polyethylene terephthalate (PET) are used. By using these thermoplastic resins, the filament of the present invention can be suitably used for producing a three-dimensional structure.

When the filament of the present invention is irradiated with ultraviolet light, the filament emits light in a color corresponding to the contained luminescent material.
The ultraviolet light referred to here is light of a wavelength of 280 nm to 410 nm, and particularly preferably light of a wavelength of 300 to 375 nm. Therefore, a blue LED (light emitting diode), a purple LED, a black light or the like can be suitably used as a light source.

The filaments of the invention may further comprise visible pigments in addition to the luminescent material.
The filaments of the present invention may contain pigments, paints, etc. that are commonly used in the field of 3D printers, as visible pigments to provide colors that are visible under natural light or fluorescent light. Examples of these visible pigments include, but are not particularly limited to, titanium oxide, carbon black, bengala, and polyazo yellow. These visible pigments can be present in amounts ranging from 0.1 to 5% by weight, based on the total weight of the filaments of the invention.
By further including these visible pigments, it is possible to determine the color tone of the three-dimensional structure when not irradiated with ultraviolet light.

  The filaments of the invention may further comprise other additives commonly used in the 3D printer field. As other additives, dispersants, surfactants, sensitizers, solvents, penetration enhancers, wetting agents, fixing agents, preservatives, antioxidants, chelating agents, pH adjusters, thickeners, aggregation inhibitors And antifoam agents.

Next, the method for producing the filament of the present invention will be described.
First, the above-mentioned light-emitting substance, if necessary, a visible pigment is dissolved in a thermoplastic resin.
The method and temperature conditions for dissolving the visible pigment and the light emitting substance according to the present invention in a thermoplastic resin are not particularly limited, and they may be dissolved rapidly by putting them in powder form (for example, 50 to 100 mesh) Also, it may be dissolved in a certain size without being powdered.
The filaments of the present invention also include those produced by adding visible pigments and luminescent materials according to the present invention to filaments generally available for three-dimensional printing.

  The filament of the present invention produces, for example, a filament containing a light-emitting material that emits red, blue, green, yellow, purple, and white, respectively, and the consumer adjusts the desired emission color by using these six types of filaments. It may be sold as a three-dimensional structure manufacturing set.

As an example of the method of determining the color of a three-dimensional structure created using the filament of the present invention, mention may be made of a method using a computer capable of examining RGB (red, blue, green) of any color. it can.
Specifically, first, an arbitrary color for a three-dimensional structure is determined on a computer. Then, when the color is analyzed by computer, the ratio of each of RGB appears. These RGB ratios can be used to mix red, blue, and green emitting luminescent materials to produce three-dimensional shapes having emission colors similar to any color.

  Hereinafter, the present invention will be described in more detail by way of examples of the present invention, but the present invention is not limited thereto.

<Fluorescent substance>
As E-300, the europium-based compound shown in the above-mentioned formula 1 was used. A powder (50 mesh) was used (Example 1).
As E-400, the europium-type compound shown by the said Chemical formula 2 was used. A powder (50 mesh) was used (Example 2).
As E-320, the europium-based compound shown in the above-mentioned formula 3 was used. A powder (50 mesh) was used (Example 3).
As E-420, the europium compound shown by the above-mentioned formula 4 was used. A powder (50 mesh) was used (Example 4).
The naphthalene type compound shown by said Chemical compound 5 was used as B-1400. A powder (50 mesh) was used (Example 5).
As T-300, a terbium-based compound represented by the above-mentioned formula 6 was used. A powder (50 mesh) was used (Example 6).
As T-600, a terbium-based compound represented by the above-mentioned formula 7 was used. A powder (50 mesh) was used (Example 7).

  In this example, acrylonitrile butadiene styrene copolymer (ABS) was used as a resin.

  As a comparative example, Y-700 (CI pigment yellow 35, CAS number: 8048-07-05) which is a light-emitting substance was used (Comparative Example 1).

<Manufacturing of Examples and Comparative Examples>
First, any one or a combination of two or more of the above luminescent materials was added to the ABS resin and dissolved by manual stirring to prepare a stock solution having a concentration of the luminescent material of 5%.
Thereafter, this stock solution was diluted with ABS resin and dissolved by manual stirring to make the concentration of the light-emitting substance 1%.
A resin was used in which the concentration of the light emitting substance was 1%.

Transparency Test of Luminescent Material under Non-UV Irradiation
Using Examples 1 to 7 and Comparative Example 1, a transparency test of the luminescent material under non-UV irradiation was performed.
Whether or not the luminescent material was colorless and transparent in the filaments of Examples 1 to 7 and Comparative Example 1 was visually measured by a fluorescent lamp under a fluorescent lamp. The results are shown in Table 1.

<Evaluation>
A visual sensory test to evaluate the transparency of the luminescent material under fluorescent light was conducted by five panelists (panelists A, B, C, D, E), and evaluated in three steps as follows. The average is shown in Table 1.
Rating 3: Luminescent substance is completely colorless and transparent.
Rating 2: Luminescent substance has a pale milky white color.
Rating 1: Luminescent substance has a thick milky white color.

  In Table 1, "actual" means an example, and "ratio" means a comparative example.

(result)
As shown in Table 1, Comparative Example 1 containing a conventional luminescent material clearly exhibited milky white color under a fluorescent lamp, and affected the color tone under non-UV irradiation.
On the other hand, Examples 1-7 were relatively high in transparency and did not affect the color tone under non-UV irradiation.
Among the examples, Examples 3 and 4 which are liquid europium compounds at normal temperature were particularly high in transparency.

  Filaments for three-dimensional printing according to the present invention are usually colorless and transparent, and by adding a luminescent material visible at the time of ultraviolet irradiation, filaments for three-dimensional printing capable of displaying different colors, patterns and information at the time of ultraviolet irradiation. It is suitably used as

Claims (5)

Acrylonitrile butadiene styrene copolymer, polylactic acid, polypropylene, polystyrene, high impact polystyrene, styrene butadiene, thermoplastic polyester elastomer, thermoplastic polyurethane, polycarbonate, polymethyl methacrylate resin, soft acrylic and polyethylene terephthalate 1 seed or more resins, and europium compounds emitting red light under ultraviolet radiation, naphthalene compound which emits blue light, and at least one selected from terbium compound emitting green light, non-UV irradiated under a dispersed in the resin Luminescent material, which is colorless and transparent ,
A filament for three-dimensional printing, including
A filament for three-dimensional printing, which emits light when irradiated with ultraviolet light. The filament for three-dimensional printing according to claim 1, wherein the europium-based compound is a compound represented by any one of the following formulas (1) to (4).
The said naphthalene type compound is a compound shown by following Chemical formula 5, The filament for three-dimensional printing of Claim 1 or 2 characterized by the above-mentioned.
The filament for three-dimensional printing according to any one of claims 1 to 3, wherein the terbium-based compound is a compound represented by the following formula (6) or (7).
The resin is one or more resins selected from the group consisting of polystyrene, polycarbonate, polymethyl methacrylate resin, and polyethylene terephthalate,
The filament for three-dimensional printing according to any one of claims 1 to 4, characterized in that the filament is colorless and transparent under non-ultraviolet radiation.