JP6950345B2 - Manufacturing method of 3D modeling equipment and 3D modeled objects - Google Patents

Description

The present invention relates to a three-dimensional modeling apparatus and a method for manufacturing a three-dimensional modeled object.

The three-dimensional modeling device is also called a 3D printer. As a three-dimensional modeling device, for example, a three-dimensional modeling material is arranged by an inkjet method according to the cross-sectional shape data of the three-dimensional shape, and curing by ultraviolet rays or the like is repeated to perform a three-dimensional modeling object (for example, a part of an industrial product or the like). , Toys such as dolls, etc.) are known.

In addition, a post-treatment device for reducing discoloration such as yellowing of the three-dimensional model obtained by the three-dimensional modeling device, a post-treatment method, and an optical three-dimensional model obtained by the post-treatment have also been proposed. ..

For example, Patent Document 1 states, "A housing for accommodating an optical three-dimensional model obtained by performing an optical three-dimensional modeling using a photocurable resin composition, and an optical three-dimensional object housed in the housing. An aftertreatment device for an optical three-dimensional model having a light irradiation means for irradiating the model with light; the light irradiation means contains light having a wavelength in the range of 430 to 500 nm and has a wavelength of 400 nm or less. A light irradiating means for irradiating an optical three-dimensional object with light that does not contain light; and a means for adjusting the distance between the optical three-dimensional object housed in the housing and the light irradiating means. A post-treatment device for an optically three-dimensional object characterized by having; ”has been proposed.

Further, Patent Document 2 states that "an optical three-dimensional model obtained by performing optical three-dimensional modeling using a photocurable resin composition contains light having a wavelength in the range of 430 to 500 nm and has a wavelength. An optical solid that does not contain light of 400 nm or less is irradiated so that the total irradiation intensity of light having a wavelength of 430 to 500 nm on the surface of the optical three-dimensional object is 15 W / m ^{2 or more.} A method of processing a modeled object. "

Further, Patent Document 3 states that "an optical three-dimensional model obtained by performing optical three-dimensional modeling using a photocurable resin composition is provided with light having a wavelength in the range of 430 to 500 nm. It was obtained by irradiation treatment so that the total irradiation intensity of light with a wavelength of 430 to 500 nm on the surface of the modeled object was 15 W / m ² or more, and the spectral transmittance obtained by measuring with a spectrophotometer was obtained. An optical three-dimensional model having an auxiliary illumination C and a yellowness of 2.4 or less at a thickness of 5 mm obtained under the condition of an auxiliary illumination C and a field of view of 2 degrees by numerical calculation by the method specified in JIS-K7373 is proposed. " ing.

Japanese Unexamined Patent Publication No. 2014-8765 Japanese Unexamined Patent Publication No. 2010-260230 Japanese Unexamined Patent Publication No. 2014-820

The three-dimensional modeling apparatus includes, for example, a discharge unit that accommodates and discharges the three-dimensional modeling material, and a light irradiation unit that irradiates the discharged three-dimensional modeling material with light. Then, in the case of manufacturing a three-dimensional model by the three-dimensional modeling device, for example, after forming a cured product of the layer of the three-dimensional modeling material by discharging the three-dimensional modeling material and irradiating light, the cured product is placed on the obtained cured product. The three-dimensional modeling material is further discharged and irradiated with light repeatedly. Then, by repeating this, the cured product of the layer of the three-dimensional modeling material is laminated, and the three-dimensional modeling product is obtained.
However, a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator is used as the three-dimensional modeling material, and the light irradiation unit irradiates only light having a wavelength of less than 400 nm. The three-dimensional model formed by the device may undergo yellowing over time.

An object of the present invention is a discharge portion that accommodates a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator and discharges the three-dimensional modeling material, and 400 nm in the discharged three-dimensional modeling material. To provide a three-dimensional modeling apparatus capable of obtaining a three-dimensional molded object in which the occurrence of yellowing over time is suppressed as compared with a three-dimensional modeling apparatus having only a light irradiation unit that irradiates light having a wavelength less than that. Is.

The above problem is solved by the following means.

The invention according to <1> is
A discharge unit that accommodates a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator and discharges the three-dimensional modeling material.
A first visible light irradiation unit that irradiates the discharged three-dimensional modeling material with visible light having a wavelength of 400 nm or more and 430 nm or less.
A three-dimensional modeling device equipped with.

The invention according to <2> is
The three-dimensional modeling according to <1> , further comprising a second visible light irradiation unit that irradiates the three-dimensional modeling material irradiated with visible light by the first visible light irradiation unit with visible light having a wavelength of 500 nm or more. Device.
The invention according to <3> is
The first visible light irradiation unit is a light irradiation unit that irradiates visible light having a wavelength of 403 nm or more and 428 nm or less, and the second visible light irradiation unit irradiates visible light having a wavelength of 500 nm or more and 580 nm or less. The three-dimensional modeling apparatus according to <2> , which is a light irradiation unit.

The invention according to <4> is
The three-dimensional modeling apparatus according to <1> , further comprising an ultraviolet light irradiation unit that irradiates the discharged three-dimensional modeling material with ultraviolet light having a wavelength of less than 400 nm.
The invention according to <5> is
The first visible light irradiation unit is a light irradiation unit that irradiates visible light having a wavelength of 403 nm or more and 428 nm or less, and the ultraviolet light irradiation unit is a light irradiation unit that irradiates ultraviolet light having a wavelength of 360 nm or more and 390 nm or less. The three-dimensional modeling apparatus according to <4>.
The invention according to <6> is
The three-dimensional according to <4> or <5> , wherein the first visible light irradiation unit is a light irradiation unit that irradiates the three-dimensional modeling material irradiated with ultraviolet light by the ultraviolet light irradiation unit with visible light. Modeling equipment.

The invention according to <7> is
The acylphosphine oxide-based photopolymerization initiator contains at least one of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide <1> to <. three-dimensional modeling apparatus according to any one of 6>.
The invention according to <8> is
The three-dimensional modeling apparatus according to <7> , wherein the content of the acylphosphine oxide-based photopolymerization initiator with respect to the entire three-dimensional modeling material is 2% by mass or more and 4% by mass or less.

The invention according to <9> is
The three-dimensional modeling apparatus according to any one of <1> to <8> , wherein the three-dimensional modeling material is colorless and transparent or white.

The invention according to <10> is
A discharge process for discharging a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator, and
A first visible light irradiation step of irradiating the three-dimensional modeling material discharged in the discharge step with visible light having a wavelength of 400 nm or more and 430 nm or less.
A method for manufacturing a three-dimensional model having.

The invention according to <11> is
The three-dimensional modeling according to <10> , further comprising a second visible light irradiation step of irradiating the three-dimensional modeling material irradiated with visible light in the first visible light irradiation step with visible light having a wavelength of 500 nm or more. How to make things.
The invention according to <12> is
The visible light emitted in the first visible light irradiation step is visible light having a wavelength of 403 nm or more and 428 nm or less, and the visible light irradiated in the second visible light irradiation step is visible light having a wavelength of 500 nm or more and 580 nm or less. The method for manufacturing a three-dimensional model according to <11> , which is light.

The invention according to <13> is
The method for producing a three-dimensional model according to <10> , further comprising an ultraviolet light irradiation step of irradiating the three-dimensional model material discharged in the discharge step with ultraviolet light having a wavelength of less than 400 nm.
The invention according to <14> is
The first visible light irradiation step is a step of irradiating visible light having a wavelength of 403 nm or more and 428 nm or less, and the ultraviolet light irradiation step is a step of irradiating ultraviolet light having a wavelength of 360 nm or more and 390 nm or less <13. > The method for manufacturing a three-dimensional model.
The invention according to <15> is
The three-dimensional model according to <13> or <14> , wherein the first visible light irradiation step is a step of irradiating the three-dimensional modeling material irradiated with ultraviolet light by the ultraviolet light irradiation step with visible light. Manufacturing method.

The invention according to <16> is
The acylphosphine oxide-based photopolymerization initiator contains at least one of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide <10> to <. 15> The method for manufacturing a three-dimensional model according to any one of.
The invention according to <17> is
The method for producing a three-dimensional model according to <16> , wherein the content of the acylphosphine oxide-based photopolymerization initiator with respect to the entire three-dimensional model is 2% by mass or more and 4% by mass or less.

The invention according to <18> is
The method for producing a three-dimensional model according to any one of <10> to <17> , wherein the three-dimensional model is colorless and transparent or white.

According to the invention according to <1> , a discharge unit containing a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator and discharging the three-dimensional modeling material, and a discharged three-dimensional structure. A three-dimensional modeling device that can obtain a three-dimensional model that suppresses the occurrence of yellowing over time compared to a three-dimensional modeling device that has only a light irradiation unit that irradiates the modeling material with light with a wavelength of less than 400 nm. Is provided.

According to the invention according to <2> or <3> , three-dimensional modeling can be obtained in which the occurrence of yellowing over time is further suppressed as compared with the case where the second visible light irradiation unit is not provided. Equipment is provided.

According to the invention according to <4> , <5> , or <6> , a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator is contained, and the three-dimensional modeling material is discharged. Compared to a three-dimensional modeling device that has only a discharge unit and a light irradiation unit that irradiates the discharged three-dimensional modeling material with light having a wavelength of less than 400 nm, the occurrence of yellowing over time is suppressed. A three-dimensional modeling apparatus for obtaining a modeled object is provided.

According to the invention according to <7> , at least 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are used as the acylphosphine oxide-based photopolymerization initiator. Even if one type is used, a discharge portion containing a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator and discharging the three-dimensional modeling material, and a discharge portion of the discharged three-dimensional modeling material have a wavelength of 400 nm. Provided is a three-dimensional modeling apparatus capable of obtaining a three-dimensional model in which the occurrence of yellowing over time is suppressed as compared with a three-dimensional modeling apparatus having only a light irradiation unit that irradiates light having a wavelength less than that. ..
According to the invention according to <8> , even if the content of the acylphosphine oxide-based photopolymerization initiator is within the above range, the three-dimensional modeling containing the photopolymerizable compound and the acylphosphine oxide-based photopolymerization initiator is contained. Compared to a three-dimensional modeling device that has only a discharge unit that accommodates the material and discharges the three-dimensional modeling material, and a light irradiation unit that irradiates the discharged three-dimensional modeling material with only light having a wavelength of less than 400 nm, over time. Provided is a three-dimensional modeling apparatus capable of obtaining a three-dimensional model in which the occurrence of yellowing is suppressed.

According to the invention according to <9> , even if the three-dimensional modeling material is colorless and transparent or white, it accommodates the three-dimensional modeling material containing the photopolymerizable compound and the acylphosphine oxide-based photopolymerization initiator and is three-dimensional. Compared to a three-dimensional modeling device that has only a discharge unit that discharges the modeling material and a light irradiation unit that irradiates the discharged three-dimensional modeling material with only light having a wavelength of less than 400 nm, yellowing occurs over time. A three-dimensional modeling apparatus for obtaining a suppressed three-dimensional model is provided.

According to the invention according to <10> , a discharge step of discharging a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator, and a wavelength of less than 400 nm on the discharged three-dimensional modeling material. Compared with the light irradiation step of irradiating only the light of No. 1 and the method of producing a three-dimensional model having only the light, a three-dimensional model in which the occurrence of yellowing over time is suppressed can be obtained.

According to the invention according to <11> or <12> , it is possible to obtain a three-dimensional model in which the occurrence of yellowing over time is further suppressed as compared with the case where the second visible light irradiation step is not provided.

According to the invention according to <13> , <14> , or <15> , a discharge step of discharging a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator, and discharge. Compared with the light irradiation step of irradiating the three-dimensional molding material with only light having a wavelength of less than 400 nm and the manufacturing method of the three-dimensional molding having only, a three-dimensional molding in which the occurrence of yellowing over time is suppressed can be obtained. Be done.

According to the invention according to <16> or <17> , the discharge step of discharging the three-dimensional modeling material containing the photopolymerizable compound and the acylphosphine oxide-based photopolymerization initiator, and the discharged three-dimensional modeling material. Compared with the light irradiation step of irradiating only light having a wavelength of less than 400 nm and the method for producing a three-dimensional model having only light, a three-dimensional model in which the occurrence of yellowing over time is suppressed can be obtained.

According to the invention according to <18> , even if the three-dimensional modeling material is colorless and transparent or white, a discharge step of discharging the three-dimensional modeling material containing the photopolymerizable compound and the acylphosphine oxide-based photopolymerization initiator. Compared with the light irradiation step of irradiating the discharged three-dimensional modeling material with only light having a wavelength of less than 400 nm and the manufacturing method of a three-dimensional model having only light, the occurrence of yellowing over time is suppressed. The original model is obtained.

It is a schematic block diagram which shows an example of the 3D modeling apparatus which concerns on 1st Embodiment. It is a process drawing which shows an example of the manufacturing method of the three-dimensional model | object which concerns on 1st Embodiment. It is a process drawing which shows an example of the manufacturing method of the three-dimensional model | object which concerns on 1st Embodiment. It is a process drawing which shows an example of the manufacturing method of the three-dimensional model | object which concerns on 1st Embodiment. It is a schematic block diagram which shows an example of the 3D modeling apparatus which concerns on 2nd Embodiment. It is a schematic block diagram which shows an example of the 3D modeling apparatus which concerns on 3rd Embodiment.

Hereinafter, embodiments that are an example of the present invention will be described.

[Manufacturing method of three-dimensional modeling apparatus and three-dimensional modeled object according to the first embodiment]
As an example of the three-dimensional modeling apparatus according to the first embodiment, the three-dimensional modeling apparatus 101 shown in FIG. 1 will be described with reference to the drawings.
The three-dimensional modeling device 101 shown in FIG. 1 is an inkjet-type three-dimensional modeling device, and includes, for example, a modeling unit 10 and a modeling table 20.
Further, the three-dimensional modeling apparatus 101 has a three-dimensional modeling material cartridge 30 accommodating the three-dimensional modeling material 30A and a support material cartridge 32 accommodating the support material 32A (support material) so as to be attached to and detached from the apparatus. I have.

The three-dimensional modeling material cartridge 30 contains a three-dimensional modeling material 30A containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator. Further, the support material cartridge 32 contains a support material 32A for forming a support portion (support portion) that is cured by light irradiation to support at least a part of the three-dimensional modeled object. Details of the three-dimensional modeling material 30A and the support material 32A used as needed will be described later.
In FIG. 1, MD indicates a three-dimensional model formed by the three-dimensional model 30A, and SP indicates a support portion formed by the support material 32A.

The modeling unit 10 is, for example, moved on the modeling area of the modeling table 20 in the main scanning direction and the sub-scanning direction intersecting (for example, orthogonal to) the main scanning direction by a driving device (not shown) (so-called carriage method). It has become.
On the other hand, the modeling table 20 has a surface having a modeling region in which a three-dimensional modeling material 30A and a support material 32A are discharged by a drive device (not shown) to form a three-dimensional modeled object.

The modeling unit 10 includes, for example, a three-dimensional modeling material discharge head 12 that discharges droplets of the three-dimensional modeling material 30A, a support material discharge head 14 that discharges droplets of the support material 32A, and the discharged three-dimensional modeling material. A light irradiation device 16 (first visible light irradiation unit) for irradiating 30A and the support material 32A with visible light having a wavelength of 400 nm or more and 430 nm or less is provided in this order. In addition, although not shown, the modeling unit 10 removes and flattens the excess three-dimensional modeling material 30A and support material 32A from, for example, the three-dimensional modeling material 30A and the support material 32A discharged onto the modeling table 20. It may be provided with a rotating roller.

The three-dimensional modeling material discharge head 12 is connected to, for example, the three-dimensional modeling material cartridge 30 through a supply pipe (not shown). Then, the three-dimensional modeling material 30A is supplied from the three-dimensional modeling material cartridge 30 to the three-dimensional modeling material discharge head 12 through a supply pipe (not shown). That is, the discharge portion of the three-dimensional modeling material 30A is composed of the three-dimensional modeling material cartridge 30, the three-dimensional modeling material 30A housed in the three-dimensional modeling material cartridge 30, and the three-dimensional modeling material discharge head 12.

Similarly, the support material discharge head 14 is also connected to the support material cartridge 32 through a supply pipe (not shown), and the support material 32A is discharged from the support material cartridge 32 through a supply pipe (not shown). It is supplied to the head 14. That is, the support material cartridge 32, the support material 32A, and the support material discharge head 14 constitute a discharge portion of the support material 32A.

A piezo type (piezoelectric method) discharge head that discharges droplets of each material by pressure is applied to the three-dimensional modeling material discharge head 12 and the support material discharge head 14, respectively. Each discharge head is not limited to this, and may be a discharge head of a type that discharges each material by the pressure of the pump.

Each of the three-dimensional modeling material discharge head 12 and the support material discharge head 14 has a short shape in which the effective discharge area (the arrangement area of the nozzle for discharging the three-dimensional modeling material and the support material) is smaller than the modeling area of the modeling table 20. It is a discharge head of.
In the three-dimensional modeling material discharge head 12 and the support material discharge head 14, for example, an effective discharge area (arrangement area of the nozzle for discharging the three-dimensional modeling material and the support material) is a modeling area on the modeling table 20. It may be a long head having a width (length in a direction intersecting (for example, orthogonal) with the moving direction (main scanning direction) of the modeling unit 10) or more.

As the light irradiation device 16, a light irradiation device that irradiates at least visible light having a wavelength of 400 nm or more and 430 nm or less is used. As a specific example of the light irradiation device 16, for example, a device having a light source such as a laser or an LED (light emitting diode) is applied.

Next, the operation of the three-dimensional modeling apparatus 101 (method for manufacturing a three-dimensional modeled object) will be described.
First, from the three-dimensional CAD (Computer Aided Design) data of a three-dimensional model formed by, for example, a three-dimensional modeling material 30A using a computer (not shown) or the like, as data for three-dimensional modeling, for example, a three-dimensional model is obtained. Generate two-dimensional shape data (slice data) for formation. At this time, two-dimensional shape data (slice data) for forming the support portion by the support material 32A is also generated. In the two-dimensional shape data for forming the support part, the width of the modeled object at the upper position is larger than the width of the modeled object at the lower position, and if there is a so-called overhanging part, this overhanging part is displayed from below. A support portion is formed so as to support it.

Next, based on the two-dimensional shape data for forming the three-dimensional modeled object, while moving the modeling unit 10, the three-dimensional modeling material 30A is discharged from the three-dimensional modeling material discharge head 12 and is placed on the modeling table 20. In addition, a layer of the three-dimensional modeling material 30A is formed (discharge step). Then, the light irradiation device 16 irradiates the layer of the three-dimensional modeling material 30A with light to cure the three-dimensional modeling material 30A to form a layer to be a part of the three-dimensional modeling object (first visible light irradiation). Process).

If necessary, based on the two-dimensional data for forming the support portion, while moving the modeling unit 10, the support material 32A is discharged from the support material discharge head 14, and three-dimensional modeling is performed on the modeling table 20. A layer of support material 32A is formed adjacent to the layer of material 30A. Then, the light irradiation device 16 irradiates the layer of the support material 32A with light to cure the support material 32A to form a layer to be a part of the support portion.
In this way, the first layer LAY1 including a layer that becomes a part of the three-dimensional model and, if necessary, a layer that becomes a part of the support portion is formed (see FIG. 2). Here, in FIG. 2, MD1 indicates a layer that becomes a part of the three-dimensional model in the first layer LAY1, and SP1 indicates a layer that becomes a part of the support portion in the first layer LAY1.

Next, the modeling table 20 is lowered. The lowering of the modeling table 20 is the thickness of the second layer (the second layer consisting of a layer that becomes a part of the three-dimensional model and, if necessary, a layer that becomes a part of the support portion) to be formed next. Minutes.

Next, similarly to the first layer LAY1, a second layer LAY2 including a layer that becomes a part of the three-dimensional model and, if necessary, a layer that becomes a part of the support portion is formed (see FIG. 3). ). Here, in FIG. 3, MD2 shows a layer that becomes a part of the three-dimensional model in the second layer LAY2, and SP2 shows a layer that becomes a part of the support portion in the second layer LAY2.

Then, the operation of forming the first layer LAY1 and the second layer LAY2 is repeatedly performed to form up to the nth layer LAYn. As a result, a three-dimensional model is formed in which at least a part is supported by the support portion (see FIG. 4). Here, in FIG. 4, MDn indicates a layer that becomes a part of the three-dimensional model in the nth layer LAYn. MD indicates a three-dimensional model. SP indicates a support unit.

After that, when the support portion is removed from the three-dimensional model, the target three-dimensional model can be obtained. Here, for removing the support portion, for example, a method of removing by hand (breakaway method), a method of injecting gas or liquid to remove the support portion, or the like is adopted.
The obtained three-dimensional model may be subjected to post-treatment such as polishing treatment.

As described above, the three-dimensional modeling device 101 of the first embodiment is a light irradiation device 16 (first visible light irradiation unit) that irradiates the discharged three-dimensional modeling material 30A with visible light having a wavelength of 400 nm or more and 430 nm or less. ). Therefore, compared to a three-dimensional modeling device equipped with only a light irradiation device that irradiates only light having a wavelength of less than 400 nm as a light irradiation device (light irradiation unit), a three-dimensional model in which yellowing over time is suppressed. Is obtained.

In the conventional three-dimensional modeling device, as a light irradiation device for curing a three-dimensional modeling material, a light irradiation device that mainly irradiates light having a wavelength of less than 400 nm has been applied. However, the three-dimensional model manufactured by the above-mentioned conventional three-dimensional modeling device can obtain a yellowed three-dimensional model, or light such as sunlight (for example, ultraviolet light, etc.) even if it is not yellowed at the time of manufacture. ) May cause yellowing over time. In particular, in a conventional three-dimensional modeling apparatus using a three-dimensional modeling material 30A containing an acylphosphine oxide-based photopolymerization initiator as a photopolymerization initiator, yellowing of the three-dimensional model is more likely to occur.

On the other hand, the three-dimensional model manufactured by using the three-dimensional modeling device 101 of the first embodiment is a tertiary model manufactured by the conventional three-dimensional modeling device even when irradiated with sunlight (particularly ultraviolet rays). A three-dimensional model in which the yellowing over time is suppressed as compared with the original model can be obtained. The reason is not clear, but it is presumed as follows.

The photopolymerization initiator absorbs ultraviolet rays and activates to start a reaction with radical molecules and hydrogen ions. The substance undergoes decomposition and reacts with resin components such as monomers and oligomers. In yellowing, radicals are generated by light. It is thought that it occurs by changing to the structure of colored objects.
The acylphosphine oxide-based photopolymerization initiator is a photopolymerization initiator that has less yellowish tint at the time of curing, but when the wavelength of the light source to be irradiated for curing is set to, for example, 365 nm ultraviolet light, it is irradiated as compared with visible light. Since the energy is high, side reactions are likely to occur, and it is considered that the yellow component is generated from the modification of the acylphosphine oxide-based photopolymerization initiator.
On the other hand, when the wavelength of the light source to be irradiated is 400 nm or more, the energy is lower than that of ultraviolet light of 365 nm, and the acylphosphine oxide-based photopolymerization initiator is activated to activate the acylphosphine oxide-based light. It is considered that yellowing, which is a side reaction, is unlikely to occur because the polymerization reaction in which the cross-linking reaction proceeds mainly occurs when the polymerization initiator decomposes, decolorizes, and reacts with resin components such as monomers and oligomers.

As described above, the three-dimensional model manufactured by using the three-dimensional modeling apparatus 101 of the first embodiment is formed while curing the three-dimensional modeling material 30A by irradiation with visible light having a wavelength of 400 nm or more and 430 nm or less. It is presumed that yellowing is unlikely to occur over time even if it is irradiated with sunlight (particularly ultraviolet rays) after production.

Further, as described above, when the three-dimensional model manufactured by the conventional three-dimensional model device turns yellow, the yellowed three-dimensional model is subjected to post-treatment by irradiating the yellowed three-dimensional model with light having a wavelength of 430 nm to 500 nm. , A method of eliminating discoloration is disclosed.
However, for example, when the three-dimensional model has a thickness (for example, the thickness is 4 mm or more) and is translucent (for example, the transmittance of visible light at a thickness of 4 mm is 60% or more and 80% or less), the irradiation is performed in the post-treatment. The light does not reach the inside of the three-dimensional model, and it may be difficult to eliminate the discoloration inside.
On the other hand, in the three-dimensional modeling apparatus 101 of the first embodiment, the layer of the three-dimensional modeling material 30A is irradiated with visible light having a wavelength of 400 nm or more and 430 nm or less, and cured while suppressing yellowing. By doing so, a three-dimensional model is formed. Therefore, as compared with the case where the post-treatment is performed after manufacturing with the conventional three-dimensional modeling apparatus as described above, a three-dimensional modeled product in which yellowing is suppressed to the inside can be obtained.

In the three-dimensional modeling device 101 of the first embodiment, the wavelength of visible light irradiated to the three-dimensional modeling material 30A by the light irradiation device 16 is not particularly limited as long as it is in the range of 400 nm or more and 430 nm or less, but the three-dimensional modeling material 30A From the viewpoint of achieving both the curing of the above and the suppression of yellowing over time in the obtained three-dimensional model, it is preferably 403 nm or more and 428 nm or less, and more preferably 405 nm or more and 425 nm or less.

The light irradiated to the three-dimensional modeling material 30A by the light irradiation device 16 preferably does not contain ultraviolet light (light of 400 nm or less) from the viewpoint of suppressing yellowing of the obtained three-dimensional modeled object over time. The three-dimensional modeling apparatus 101 of the first embodiment uses a three-dimensional modeling material 30A containing an acylphosphine oxide-based photopolymerization initiator that generates radicals by absorbing light having a wavelength of 400 nm or more and 430 nm or less. Therefore, even if the light irradiated to the three-dimensional modeling material 30A by the light irradiation device 16 does not contain ultraviolet light, the three-dimensional modeling material 30A is cured by the light having a wavelength of 400 nm or more and 430 nm or less, and a three-dimensional model is formed. NS.
As a method of preventing the light irradiated to the three-dimensional modeling material 30A by the light irradiation device 16 from including ultraviolet light, for example, in addition to the method of using an LED (light emitting diode) as the light irradiation device 16, ultraviolet light Examples include a method using a filter that does not transmit light.

The three-dimensional modeling apparatus 101 of the first embodiment includes both a discharge portion of the three-dimensional modeling material 30A and a discharge portion of the support material 32A, but only the discharge portion of the three-dimensional modeling material 30A is provided as the discharge portion. It may be provided.

[Manufacturing method of three-dimensional modeling apparatus and three-dimensional modeled object according to the second embodiment]
Next, as an example of the three-dimensional modeling apparatus according to the second embodiment, the three-dimensional modeling apparatus 102 shown in FIG. 5 will be described.
The three-dimensional modeling device 102 shown in FIG. 5 is a three-dimensional modeling material 30A and a support material 32A irradiated with visible light having a wavelength of 400 nm or more and 430 nm or less by the light irradiation device 16 (first visible light irradiation unit) at 500 nm. It is a form having a light irradiation device 18 (second visible light irradiation unit) that irradiates visible light having the above wavelengths.
That is, the three-dimensional modeling device 102 shown in FIG. 5 includes a modeling unit 11 having a three-dimensional modeling material discharge head 12, a support material discharge head 14, a light irradiation device 16, and a light irradiation device 18 in this order. It is the same as the three-dimensional modeling apparatus 101 of the first embodiment except that the three-dimensional modeling apparatus 101 is used.
The same members and the like as those of the three-dimensional modeling apparatus 101 shown in FIG. 1 are designated by the same reference numerals as those in FIG. 1, and the description thereof will be omitted.

As the light irradiation device 18, a light irradiation device that irradiates at least visible light having a wavelength of 500 nm or more is used. As a specific example of the light irradiation device 18, for example, a device having a light source such as a laser or an LED (light emitting diode) is applied.

In the three-dimensional modeling apparatus 102, while moving the modeling unit 10, the three-dimensional modeling material 30A is discharged from the three-dimensional modeling material discharge head 12 to form a layer of the three-dimensional modeling material 30A on the modeling table 20 (discharging step). ). Then, along with the formation of the layer of the three-dimensional modeling material 30A, the support material 32A is discharged from the support material discharge head 14 while moving the modeling unit 10 as necessary, and the three-dimensional modeling material 30A is placed on the modeling table 20. A layer of support material 32A is formed adjacent to the layer.
Next, the light irradiation device 16 irradiates the layer of the three-dimensional modeling material 30A and the support material 32A formed as needed with light and cures the three-dimensional modeling object and, if necessary, formed. A layer to be a part of the support portion is formed (first visible light irradiation step). After that, the light irradiation device 18 irradiates the three-dimensional model and the layer that becomes a part of the support portion formed as needed with light (second visible light irradiation step).

Then, while lowering the modeling table 20, the three-dimensional modeling material 30A is discharged, the support material 32A is discharged as necessary, the curing is performed by light irradiation from the light irradiation device 16, and the light irradiation by the light irradiation device 18 is repeated. conduct. As described above, a three-dimensional model and a support portion formed as needed can be obtained. As in the first embodiment, when the support unit is provided, the support unit is removed as necessary.

As described above, the three-dimensional modeling device 102 of the second embodiment is a light irradiation device 16 (first visible light irradiation unit) that irradiates the discharged three-dimensional modeling material 30A with visible light having a wavelength of 400 nm or more and 430 nm or less. ), The three-dimensional modeling material 30A irradiated with visible light by the light irradiation device 16 is provided with a light irradiation device 18 (second visible light irradiation unit) that irradiates visible light having a wavelength of 500 nm or more. Therefore, as compared with the three-dimensional modeling device that does not have the light irradiation device 18, a three-dimensional modeled object in which yellowing over time is further suppressed can be obtained.

In the three-dimensional modeling device 102 of the second embodiment, the wavelength of visible light irradiated to the three-dimensional modeling material 30A by the light irradiation device 16 is not particularly limited as long as it is in the range of 400 nm or more and 430 nm or less, but the three-dimensional modeling material 30A From the viewpoint of achieving both the curing of the above and the suppression of yellowing over time in the obtained three-dimensional model, it is preferably 403 nm or more and 428 nm or less, more preferably 405 nm or more and 425 nm or less, and further preferably 405 nm or more and 420 nm or less.
The wavelength of visible light irradiated to the three-dimensional modeling material 30A by the light irradiation device 18 is not particularly limited as long as it is 500 nm or more, but from the viewpoint of suppressing yellowing over time in the three-dimensional modeled object, it is 500 nm or more and 580 nm or less. It is preferably 505 nm or more and 525 nm or less, more preferably.
Both the light irradiating the three-dimensional modeling material 30A by the light irradiating device 16 and the light irradiating the three-dimensional modeling material 30A by the light irradiating device 18 suppress yellowing over time in the obtained three-dimensional modeling object. From the viewpoint, it is preferable not to contain ultraviolet light (light of 400 nm or less).

[Manufacturing method of three-dimensional modeling apparatus and three-dimensional modeled object according to the third embodiment]
Next, as an example of the three-dimensional modeling apparatus according to the third embodiment, the three-dimensional modeling apparatus 103 shown in FIG. 6 will be described.
The three-dimensional modeling device 103 shown in FIG. 6 has a light irradiation device 19 (ultraviolet light irradiation unit) that irradiates the discharged three-dimensional modeling material 30A and the support material 32A with ultraviolet light having a wavelength of less than 400 nm. Then, in the three-dimensional modeling device 103, the three-dimensional modeling material 30A and the support material 32A irradiated with ultraviolet light having a wavelength of less than 400 nm by the light irradiation device 19 are subjected to the light irradiation device 16 (first visible light irradiation unit). It irradiates visible light with a wavelength of 400 nm or more and 430 nm or less.
That is, the three-dimensional modeling device 103 shown in FIG. 6 includes a modeling unit 13 having a three-dimensional modeling material discharge head 12, a support material discharge head 14, a light irradiation device 19, and a light irradiation device 16 in this order. It is the same as the three-dimensional modeling apparatus 101 of the first embodiment except that the three-dimensional modeling apparatus 101 is used.
The same members and the like as those of the three-dimensional modeling apparatus 101 shown in FIG. 1 are designated by the same reference numerals as those in FIG. 1, and the description thereof will be omitted.

As the light irradiation device 19, a light irradiation device that irradiates at least ultraviolet light having a wavelength of less than 400 nm is used. Specific examples of the light irradiation device 18 include a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a deep ultraviolet lamp, a lamp that excites a mercury lamp from the outside without an electrode using microwaves, an ultraviolet laser, a xenon lamp, and a UV-LED. A device having a light source such as (ultraviolet light emitting diode) is applied.

In the three-dimensional modeling apparatus 103, while moving the modeling unit 10, the three-dimensional modeling material 30A is discharged from the three-dimensional modeling material discharge head 12 to form a layer of the three-dimensional modeling material 30A on the modeling table 20 (discharging step). ). Then, along with the formation of the layer of the three-dimensional modeling material 30A, the support material 32A is discharged from the support material discharge head 14 while moving the modeling unit 10 as necessary, and the three-dimensional modeling material 30A is placed on the modeling table 20. A layer of support material 32A is formed adjacent to the layer.
Next, the light irradiation device 19 and the light irradiation device 16 irradiate the layer of the three-dimensional modeling material 30A and the support material 32A formed as needed with light to cure the three-dimensional modeling object and, if necessary. A layer that becomes a part of the support portion formed accordingly is formed (ultraviolet light irradiation step and first visible light irradiation step).

Then, while lowering the modeling table 20, the three-dimensional modeling material 30A is discharged, the support material 32A is discharged as necessary, and the light irradiation from the light irradiation device 19 and the curing by the light irradiation from the light irradiation device 16 are repeated. To do. As described above, a three-dimensional model and a support portion formed as needed can be obtained. As in the first embodiment, when the support unit is provided, the support unit is removed as necessary.

As described above, the three-dimensional modeling apparatus 103 of the third embodiment emits visible light having a wavelength of 400 nm or more and 430 nm or less in addition to the light irradiation apparatus 19 (ultraviolet light irradiation unit) that irradiates ultraviolet light having a wavelength of less than 400 nm. It has a light irradiation device 16 (first visible light irradiation unit) for irradiating. Therefore, like the three-dimensional modeling device 101 of the first embodiment, the three-dimensional modeling in which yellowing over time is suppressed as compared with the three-dimensional modeling device having only the light irradiation device 19 without the light irradiation device 16. You get things.

In the three-dimensional modeling device 103 of the third embodiment, the wavelength of visible light irradiated to the three-dimensional modeling material 30A by the light irradiation device 16 is not particularly limited as long as it is in the range of 400 nm or more and 430 nm or less, but the three-dimensional modeling material 30A From the viewpoint of achieving both the curing of the above and the suppression of yellowing over time in the obtained three-dimensional model, it is preferably 403 nm or more and 428 nm or less, more preferably 405 nm or more and 425 nm or less, and further preferably 405 nm or more and 420 nm or less.
The wavelength of the ultraviolet light irradiated to the three-dimensional modeling material 30A by the light irradiation device 19 is not particularly limited as long as it is less than 400 nm, but from the viewpoint of curing the three-dimensional modeling material 30A, it is preferably 360 nm or more and 395 nm or less, and 365 nm. More preferably, it is 395 nm or less.

The modeling unit 13 in the three-dimensional modeling device 103 of the third embodiment includes a three-dimensional modeling material discharge head 12, a support material discharge head 14, a light irradiation device 19, and a light irradiation device 16 in this order. However, the present invention is not limited to this, and the three-dimensional modeling material discharge head 12, the support material discharge head 14, the light irradiation device 16, and the light irradiation device 19 may be provided in this order.
Further, it may not have the support material discharge head 14, or may have the light irradiation device 18 in the three-dimensional modeling device 102 of the second embodiment. That is, a modeling unit having a three-dimensional modeling material discharge head 12, a support material discharge head 14, a light irradiation device 19, a light irradiation device 16, and a light irradiation device 18 in this order is provided, and the light irradiation device 18 provides. It may be in the form of irradiating a layer that becomes a part of a three-dimensional model with light (having a second visible light irradiation step).

[Three-dimensional modeling material and support material]
Next, the three-dimensional modeling housed in the three-dimensional modeling material cartridge 30 in the three-dimensional modeling device 101 of the first embodiment, the three-dimensional modeling device 102 of the second embodiment, and the three-dimensional modeling device 103 of the third embodiment. The material 30A will be described. Further, the support material 32A used as needed and housed in the support material cartridge 32 will also be described. Hereinafter, the reference numerals may be omitted.

<Three-dimensional modeling material>
The three-dimensional modeling material contains at least a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator, and may contain other components if necessary. Hereinafter, each component contained in the three-dimensional modeling material will be described.

(Photopolymerizable compound)
The photopolymerizable compound is a compound that polymerizes when irradiated with light, and may be any of a monomer, an oligomer, and a prepolymer, and examples thereof include a compound having a photopolymerizable group.
As the photopolymerizable compound, a compound having a photopolymerizable group may be used alone or in combination of two or more.

Examples of the photopolymerizable group include radically polymerizable groups.
In this embodiment, since an acylphosphine oxide-based photopolymerization initiator is used as the photopolymerization initiator, a compound having a radically polymerizable group is used as the photopolymerizable compound.
The photopolymerizable compound may have only one photopolymerizable group or two or more photopolymerizable groups in one molecule. Further, the compound having a photopolymerizable group may have a cationically polymerizable group in addition to the radically polymerizable group.

Examples of the radically polymerizable group include an ethylenically unsaturated double bond. Examples of the ethylenically unsaturated double bond include a (meth) acryloyl group, an N-vinyl group, and a vinyl ether group.
Examples of the cationically polymerizable group include an epoxy group, an oxetanyl group, a vinyl group and the like.

Examples of the compound having a radically polymerizable group include a compound having a (meth) acryloyl group. Moreover, as a compound having a (meth) acryloyl group, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate and the like are preferably mentioned.
In addition, in this specification, (meth) acrylate means both acrylate and methacrylate, and (meth) acrylic means both acrylic and methacrylic. Further, the (meth) acryloyl means both an acryloyl group and a methacryloyl group.
Examples of the compound having a radically polymerizable group and a cationically polymerizable group include a compound having a (meth) acryloyl group as a radically polymerizable group and a vinyl ether group as a cationically polymerizable group.

Among these, the photopolymerizable compound is more preferably a compound having a (meth) acryloyl group, and further preferably urethane (meth) acrylate.

-Urethane (meth) acrylate-
Urethane (meth) acrylate is a compound having a urethane structure and two or more (meth) acryloyl groups in one molecule. The urethane (meth) acrylate may be a monomer or an oligomer, but may be an oligomer.
The functional number of urethane (meth) acrylate (the number of (meth) acryloyl groups) is preferably 2 or more and 20 or less (preferably 2 or more and 15 or less).

Examples of the urethane (meth) acrylate include a reaction product using a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth) acrylate. Specific examples of urethane (meth) acrylate include, for example, a reaction product of a prepolymer obtained by reacting a polyisocyanate compound and a polyol compound and having an isocyanate group at the terminal, and a hydroxyl group-containing (meth) acrylate. Can be mentioned. Further, as the urethane (meth) acrylate, a reaction product of a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate can also be mentioned.

-Polyisocyanate compound Examples of the polyisocyanate compound include chain saturated hydrocarbon isocyanate, cyclic saturated hydrocarbon isocyanate, aromatic polyisocyanate and the like. Among these, as the polyisocyanate compound, a chain saturated hydrocarbon isocyanate having no light absorption band in the near-ultraviolet region and a cyclic saturated hydrocarbon isocyanate having no light absorption band in the near-ultraviolet region are preferable.
Examples of the chain saturated hydrocarbon isocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the cyclic saturated hydrocarbon isocyanate include isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate.
Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1, Examples thereof include 3-phenyldiisocyanate and 1,5-naphthalenediisocyanate.

-Polyol compound Examples of the polyol compound include diols and polyhydric alcohols.
Examples of the diol include alkylene glycols (eg, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-). Butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol , 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecandiol, 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, etc. ) Etc. can be mentioned.
Examples of the polyhydric alcohol include alkylene polyhydric alcohols containing 3 or more hydroxyl groups (eg, glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butantriol). , Erythritol, sorbitol, pentaerythritol, dipentaerythritol, mannitol, etc.).

Examples of the polyol compound include polyether polyols, polyester polyols, polycarbonate polyols and the like.

Examples of the polyether polyol include a multimer of a polyhydric alcohol, an adduct of a polyhydric alcohol and an alkylene oxide, a ring-opening polymer of an alkylene oxide, and the like.
Here, examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, and 1, 2-hexanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol , 1,9-Nonandiol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol and the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

Examples of the polyester polyol include a reaction product of a polyhydric alcohol and a dibasic acid, a ring-opening polymer of a cyclic ester compound, and the like.
Here, as the polyhydric alcohol, for example, the polyhydric alcohol exemplified in the description of the polyether polyol can be mentioned.
Examples of the dibasic acid include carboxylic acids (for example, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.), carboxylic acid anhydrides and the like.
Examples of the cyclic ester compound include ε-caprolactone and β-methyl-δ-valerolactone.

Examples of the polycarbonate polyol include a reaction product of glycol and alkylene carbonate, a reaction product of glycol and diaryl carbonate, and a reaction product of glycol and dialkyl carbonate.
Here, examples of the alkylene carbonate include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate and the like.
Examples of the diaryl carbonate include diphenyl carbonate, 4-methyldiphenyl carbonate, 4-ethyldiphenyl carbonate, 4-propyldiphenyl carbonate, 4,4'-dimethyldiphenyl carbonate, 2-tolyl-4-tolyl carbonate, 4,4'. Examples thereof include −diethyldiphenyl carbonate, 4,4′-dipropyldiphenyl carbonate, phenyltoluyl carbonate, bischlorophenyl carbonate, phenylchlorophenyl carbonate, phenylnaphthyl carbonate, dinaphthyl carbonate and the like.
Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, and diisoamyl carbonate. And so on.

-Hydrogen group-containing (meth) acrylate Examples of the hydrogen group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy. -3-Phenoxypropyl (meth) acrylate, glycerindi (meth) acrylate, trimethylpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like can be mentioned. Examples of the hydrogen group-containing (meth) acrylate include an adduct of a glycidyl group-containing compound (for example, alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, etc.) and (meth) acrylic acid.

-Urethane (meth) acrylate weight average molecular weight-
The weight average molecular weight of the urethane (meth) acrylate is preferably 500 or more and 5000 or less, and more preferably 1000 or more and 3000 or less.
The weight average molecular weight of urethane (meth) acrylate is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

Only one type of urethane (meth) acrylate may be used, or two or more types may be used in combination. When two or more kinds of urethane (meth) acrylates are used in combination, it is preferable to use at least one kind of polyester urethane (meth) acrylate having a polyester skeleton and polyether urethane (meth) acrylate having a polyether skeleton.
Examples of the content of the polyester-based urethane (meth) acrylate and the polyether-based urethane (meth) acrylate with respect to the entire urethane (meth) acrylate include 1% by mass or more and 99% by mass or less, and 2% by mass or more and 98% by mass or less. Is preferable. The blending amount is adjusted according to the desired viscosity of the three-dimensional modeling material.

Further, as the photopolymerizable compound, urethane (meth) acrylate and other photopolymerizable compounds described later may be used in combination.
When the urethane (meth) acrylate is used in combination with another photopolymerizable compound, the content of the urethane (meth) acrylate in the entire photopolymerizable compound is, for example, 1% by mass or more and 99% by mass or less, and 2% by mass. % Or more and 98% by mass or less is preferable. The blending amount is adjusted according to the desired viscosity of the three-dimensional modeling material.

-Other photopolymerizable compounds-
Other photopolymerizable compounds are not particularly limited, and examples thereof include other (meth) acrylates other than urethane (meth) acrylate.
Examples of other (meth) acrylates include monofunctional (meth) acrylates and polyfunctional (meth) acrylates.

Examples of the monofunctional (meth) acrylate include a linear, branched, or cyclic alkyl (meth) acrylate, a (meth) acrylate having a hydroxyl group, a (meth) acrylate having a heterocycle, and a (meth) acrylamide compound. And so on.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl. Examples thereof include (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.

Examples of the (meth) acrylate having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and methoxypolyethylene glycol mono (meth) acrylate. Examples thereof include polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol block polymer mono (meth) acrylate.

Examples of the (meth) acrylate having a heterocycle include tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, and 4- (meth) acryloyloxy. Examples thereof include methyl-2-cyclohexyl-1,3-dioxolane and adamantyl (meth) acrylate.
Examples of the (meth) acrylamide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N. Included are'-dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide and the like.

Among the polyfunctional (meth) acrylates, the bifunctional (meth) acrylate includes, for example, 1,10-decanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, and the like. 2-Butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,7-heptanediol Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate ) Acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 2- (2- (2-) Vinyloxyethoxy) ethyl (meth) acrylate, EO (ethylene oxide) modified bisphenol A di (meth) acrylate, PO (propylene oxide) modified bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, EO (ethylene oxide) modified bisphenol F di (meth) acrylate and the like can be mentioned.

Among the polyfunctional (meth) acrylates, the trifunctional or higher functional (meth) acrylates include, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, and propoxylated trimethylol propanetri (meth) acrylate. Meta) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, EO (ethylene oxide) modified diglycerin tetra (meth) ) Acrylate, ditrimethylolpropane tetra (meth) acrylate-modified acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

Only one kind of other photopolymerizable compound may be used, or two or more kinds may be used.
When a urethane (meth) acrylate is used in combination with another photopolymerizable compound, the other photopolymerizable compound includes a compound having a (meth) acryloyl group and a vinyl ether group (for example, 2- (2-vinyloxyethoxy)). Ethyl (meth) acrylate) is preferred.

-Content of photopolymerizable compound-
The content of the photopolymerizable compound (when a plurality of types of photopolymerizable compounds are used in combination, the total content of the plurality of types of photopolymerizable compounds) is, for example, 70% by mass with respect to the entire three-dimensional modeling material. The above is 96% by mass or less, and 80% by mass or more and 96% by mass or less is preferable.

(Photopolymerization initiator)
The photopolymerization initiator is a compound that generates an active species (for example, a radical, a cation, etc.) that initiates a photopolymerization reaction of a photopolymerizable compound by light irradiation, and in the present embodiment, an acyl that generates a radical as the active species. A phosphine oxide-based photopolymerization initiator is used.
The acylphosphine oxide-based photopolymerization initiator is a compound in which a carbon atom of an acyl group and a phosphorus atom of a phosphine oxide group are directly bonded to each other. By absorbing light, the bond between the carbon atom and the phosphorus atom is dissociated. Radicals are generated.

Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, IRGACURE TPO) and bis (2,4,6-trimethylbenzoyl)-. Examples thereof include phenylphosphine oxide (manufactured by BASF, IRGACURE 819).
Hereinafter, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is also referred to as "TPO", and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is also referred to as "BAPO".
A three-dimensional model manufactured by using a conventional three-dimensional model containing a three-dimensional model containing at least one of TPO and BAPO is particularly prone to yellowing over time. However, as described above, if the three-dimensional modeling apparatus is provided with the discharge unit that accommodates and discharges the three-dimensional modeling material and the first visible light irradiation unit, yellowing over time is suppressed. A model is obtained.

The content of the acylphosphine oxide-based photopolymerization initiator in the entire three-dimensional modeling material includes, for example, 1% by mass or more and 5% by mass or less, preferably 2% by mass or more and 4% by mass or less, and 3% by mass or more and 4% by mass. % Or less is more preferable.
In particular, a three-dimensional model manufactured by using a conventional three-dimensional modeling device containing a three-dimensional modeling material in which the total content of TPO and BAPO is 3% by mass or more with respect to the entire three-dimensional modeling material is over time. Yellowing is likely to occur. However, as described above, if the three-dimensional modeling apparatus is provided with the discharge unit that accommodates and discharges the three-dimensional modeling material and the first visible light irradiation unit, yellowing over time is suppressed. A model is obtained.

In addition, as the photopolymerization initiator, other photopolymerization initiators (that is, photoradical polymerization initiators other than acylphosphine oxide-based photopolymerization initiators, photocationic polymerization initiators) may be used in combination.
Among other photopolymerization initiators, photoradical polymerization initiators other than acylphosphine oxide-based photopolymerization initiators include, for example, acetophenones, benzoins, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, and the like. Examples thereof include peroxides, 2,3-alkyldione compounds, disulfide compounds, fluoroamine compounds and aromatic sulfoniums.
Among other photopolymerization initiators, the photocationic polymerization initiator includes, for example, a diazonium salt, an iodonium salt (diaryliodonium salt, etc.), a sulfonium salt (triarylsulfonium salt, etc.), an iron arene complex, and an organic polyhalogen. Examples include compounds.
The content of the other photopolymerization initiator is, for example, preferably 2% by mass or less, more preferably 1% by mass or less, based on the entire three-dimensional modeling material.

(Other ingredients)
-Colorant-
The three-dimensional modeling material may contain a colorant as another component, if necessary.
As will be described later, examples of the three-dimensional modeling material include a colorless and transparent three-dimensional modeling material and a white three-dimensional modeling material.
When the 3D modeling material is colorless and transparent, the 3D modeling material does not contain a colorant, or the content of the colorant is 0.1% by mass or less (more preferably 0.) With respect to the entire 3D modeling material. 05% by mass or less, more preferably 0.01% by mass or less).

When the three-dimensional modeling material is white, it is preferable that the three-dimensional modeling material contains a white colorant.
Examples of the white colorant include white pigments such as titanium dioxide, zirconium oxide, calcium carbonate, barium sulfate, silicon oxide, magnesium oxide, aluminum oxide, tin oxide, kaolin and talc.
The content of the white colorant in the entire three-dimensional modeling material when the three-dimensional modeling material is white includes, for example, 0.01% by mass or more and 50% by mass or less, and 0.05% by mass or more and 20% by mass. % Or less is preferable, and 0.1% by mass or more and 10% by mass or less is more preferable.
Further, the white three-dimensional modeling material does not contain a coloring agent other than white, or the content of the coloring agent other than white is 0.1% by mass or less (more preferably 0.) With respect to the entire three-dimensional modeling material. 05% by mass or less, more preferably 0.01% by mass or less).
Examples of the colorant other than white include a yellow colorant, a magenta colorant, a cyan colorant, a black colorant, and the like. Specific examples of the colorant other than white include azo pigments such as azo lake pigments, polycyclic pigments such as azo dyes and phthalocyanine pigments, organic pigments such as nitro pigments, and inorganic pigments such as carbon black.

-Polymerization inhibitor-
The three-dimensional modeling material may contain a polymerization inhibitor, if necessary.
Examples of the polymerization inhibitor include phenolic polymerization inhibitors (eg, p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2'-methylenebis (for example). 4-Methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), etc.), hindered amines, hydroquinone Well-known polymerization inhibitors such as monomethyl ether (MEHQ) and hydroquinone can be mentioned.
The content of the polymerization inhibitor is preferably, for example, 0.1 part by mass or more and 30 parts by mass or less, and more preferably 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the photopolymerizable compound.
The polymerization inhibitor may be used alone or in combination of two or more.

-Surfactant-
The three-dimensional modeling material may contain a surfactant, if necessary.
Examples of the surfactant include silicone-based surfactants, acrylic-based surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, and fluorine-based surfactants. Well-known surfactants can be mentioned.
The content of the surfactant is preferably 0.05% by mass or more and 15% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less with respect to the entire three-dimensional modeling material.
The surfactant may be used alone or in combination of two or more.

-Oxygen scavenger-
The three-dimensional modeling material may contain an oxygen scavenger, if necessary.
Examples of the oxygen scavenger include amine-based oxygen scavengers and organophosphorus-based oxygen scavengers.
The amine-based oxygen scavenger is an oxygen scavenger having an amino group, and examples thereof include ethyl 4- (dimethylamino) benzoate.
The organophosphorus oxygen scavenger is an oxygen scavenger having a phosphorus atom, and examples thereof include triphenylphosphine (TPP) and triethylphosphite (TEP).
When the three-dimensional modeling material contains an oxygen scavenger, the content of the oxygen scavenger is preferably 3 parts by mass or more and 50 parts by mass or less, and 5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the photopolymerization initiator. More preferred.
The oxygen scavenger may be used alone or in combination of two or more.

-Photosensitizer-
The three-dimensional modeling material may contain a photosensitizer. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone, thioxanthone, and the like.
When a photosensitizer is used, the content of the photosensitizer in the entire three-dimensional modeling material is, for example, 0.1% by mass or more and 10% by mass or less, and is 0 from the viewpoint of controlling the hardness of the three-dimensional modeling object. .2% by mass or more and 5% by mass or less is preferable, and 0.3% by mass or more and 3% by mass or less is more preferable.

− Other −
Other components other than the above that may be contained in the three-dimensional modeling material include, for example, solvents, fixing agents, fungicides, preservatives, antioxidants, chelating agents, thickeners, dispersants, polymerization accelerators, and permeation agents. Well-known additives such as accelerators and wetting agents (moisturizers) can be mentioned.

(Characteristics of 3D modeling material)
The three-dimensional modeling material is preferably colorless and transparent or white, and more preferably colorless and transparent or white and translucent.
A three-dimensional model manufactured by using a conventional three-dimensional model device containing a colorless transparent or white three-dimensional model material is particularly susceptible to yellowing over time. However, as described above, even if a colorless transparent or white three-dimensional modeling material is used, it may be a three-dimensional modeling apparatus provided with a discharge unit for accommodating and discharging the three-dimensional modeling material and the first visible light irradiation unit. For example, a three-dimensional model in which yellowing itself over time is suppressed can be obtained.
In particular, in the three-dimensional model manufactured using the conventional three-dimensional modeling device containing the white and translucent three-dimensional modeling material, yellowing occurred in addition to the fact that yellowing over time was easily visible. Even if light having a wavelength of 430 nm to 500 nm is irradiated later as a post-treatment, it is difficult for the light to reach the inside of the three-dimensional model. However, in the case of a three-dimensional modeling device provided with a discharge unit that accommodates and discharges a three-dimensional modeling material and the first visible light irradiation unit, a three-dimensional modeling device that is cured while suppressing yellowing is laminated to be tertiary. Since the original model is formed, a three-dimensional model in which yellowing itself over time is suppressed can be obtained.

Here, "colorless and transparent" means that the transmittance of light having a wavelength of 380 nm or more and 780 nm or less is 80% or more when the optical path length is 4 mm. Further, "semi-transparent" means that the transmittance of light having a wavelength of 380 nm or more and 780 nm or less is 60% or more and less than 80% when the optical path length is 4 mm.
The transmittance is calculated by measuring the optical path length and transmittance of the measurement sample using a spectrophotometer and correcting the optical path length based on the Beer-Lambert law.
Further, "white" means that in the CIE1976L * a * b * color system, the brightness L * is 65 or more, the hue a * is -4 or more and 1 or less, and the hue b * is -10 or more and 7 or less. Means. The lightness L *, hue a *, and hue b * are values measured using X-Rite 939 (aperture diameter 4 mm) manufactured by X-Rite.

When the three-dimensional modeling material is colorless and transparent, the transmittance of light having a wavelength of 380 nm or more and 780 nm or less when the optical path length is 4 mm is preferably 83% or more, and more preferably 85% or more. When the three-dimensional modeling material is white and translucent, the transmittance of light having a wavelength of 380 nm or more and 780 nm or less when the optical path length is 4 mm is preferably 63% or more and 78% or less.
When the three-dimensional modeling material is white, the brightness L * is preferably 70 or more, the hue a * is preferably -3 or more and 0.8 or less, and the hue b * is preferably −8 or more and 5 or less.

The viscosity of the three-dimensional modeling material is, for example, in the range of 3 mPa · s or more and 100 mPa · s or less, and is preferably 5 mPa · s or more and 30 mPa · s or less.
Here, the viscosity is a value measured using Leomat 115 (manufactured by Controles) as a measuring device under the conditions of ^{a measurement temperature of 55 ° C. and a shear rate of 1400s -1.}

The surface tension of the three-dimensional modeling material is, for example, in the range of 18 mN / m or more and 70 mN / m or less, and is preferably 20 mN / m or more and 40 mN / m or less.
Here, the surface tension is a value measured in an environment of 23 ° C. and 55% RH using a Wilhelmy type surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.).

<Support material>
The support material is used as needed, and there is no particular limitation, and a known support material is used. Examples of the support material include a material that can be cured by irradiation with visible light having a wavelength of 400 nm or more and 430 nm or less and that can be easily removed after curing. Examples include materials containing the above components and plasticizers.

Examples of the plasticizer include water and non-radiation-curable polymers. A non-radiation-curable polymer is a polymer that does not undergo a curing (polymerization) reaction due to radiation (for example, ultraviolet rays or electron beams).
Non-radiocurable polymers include, for example, polyether polyols, castor oil polyols, and polyester polyols. The non-radiation-curable polymer may be used alone or in combination of two or more.
The weight average molecular weight of the non-radiation-curable polymer is preferably 200 or more and 1000 or less, and more preferably 250 or more and 850 or less.
The weight average molecular weight of the non-radiocurable polymer is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard material.
The content of the plasticizer is, for example, 25% by mass or more and 60% by mass or less, more preferably 30% by mass or more and 50% by mass or less, and more preferably 35% by mass or more and 50% by mass or less with respect to the entire support material. ..

The surface tension of the support material is preferably in the range of 20 mN / m or more and 40 mN / m or less.
The viscosity of the support material is preferably in the range of 30 mPa · s or more and 50 mPa · s or less.

Hereinafter, the present embodiment will be described in more detail with reference to Examples and Comparative Examples, but the present embodiment is not limited to the following Examples. Unless otherwise specified, "parts" and "%" are based on mass.

<Preparation of 3D modeling material>
(Preparation of 3D modeling material 1)
Each component shown in Table 1 below was mixed to prepare a three-dimensional modeling material.
The numerical values in Table 1 mean the content (parts by mass) of the corresponding component.

The abbreviations described in Table 1 are as follows.
-U-15HA: Photopolymerizable compound (urethane acrylate oligomer, weight average molecular weight: 2300), manufactured by Shin-Nakamura Chemical Industry Co., Ltd.-U-200PA: Photopolymerizable compound (urethane acrylate oligomer, polyester urethane acrylate, weight average) Molecular weight: 2700), manufactured by Shin-Nakamura Chemical Industry Co., Ltd., UA-4200: Photopolymerizable compound (urethane acrylate oligomer, polyether urethane acrylate, weight average molecular weight: 1000), manufactured by Shin-Nakamura Chemical Industry Co., Ltd., VEEA- AI: Photopolymerizable compound (Compound name: 2- (2-vinyloxyethoxy) ethyl acrylate) manufactured by Nippon Catalyst Co., Ltd. BAPO: Acylphosphine oxide-based photopolymerization initiator (Product name: Irgacure 819, Compound name: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), manufactured by BASF

-MEHQ: Polymerization inhibitor (compound name: 4-methoxyphenol), manufactured by Wako Pure Chemical Industries, Ltd.-KAYACURE EPA: oxygen scavenger (compound name: p- (dimethylamino) benzoic acid ethyl ester), manufactured by Nippon Kayakusha Co., Ltd. TEGO Rad2011: Silicone surfactant, SF White dispersion manufactured by Ebonic: Colorant (isobornyl acrylate dispersion of titanium oxide, pigment concentration: 40% by mass), manufactured by Sanyo Dye Co., Ltd.

<Manufacturing of 3D modeling equipment>
(Manufacturing of 3D Modeling Device 1: Example 1)
As the three-dimensional modeling device 1, the three-dimensional modeling device 101 shown in FIG. 1 was manufactured.
Specifically, a Polaris head (model number: PQ512 / 85) manufactured by Fuji Film Dimatics Co., Ltd. is used as the three-dimensional modeling material discharge head 12, and a light emitting diode manufactured by Ushio, Inc. (model number: E110 II HD, model number: E110 II HD) is used as the light irradiation device 16. Wavelength: 405 nm, light emission intensity: 7 W / cm ² ) was used.
Further, the three-dimensional modeling material cartridge 30 accommodates the above-mentioned three-dimensional modeling material 1 as the three-dimensional modeling material 30A, and the support material 32A is not used.
The three-dimensional modeling device 101 is a system in which the discharge head (three-dimensional modeling material discharge head 12) and the light source (light irradiation device 16) reciprocate together, and the modeling material having a thickness of 20 μm is used for each scan. The device was formed by laminating layers and performing curing treatment by light irradiation. In addition, the three-dimensional modeling material 30A is passed through a profile star A050 filter (filtration accuracy 5 μm) manufactured by Nippon Pole via a Tyon 2375 chemical resistant tube manufactured by Saint-Gobain from a storage tank under light-shielding conditions by a liquid feed pump to pass foreign substances. After removing it, the liquid is sent to the three-dimensional modeling material discharge head.

(Manufacturing of 3D modeling apparatus 2: Example 2)
As the three-dimensional modeling device 2, the three-dimensional modeling device 102 shown in FIG. 5 was manufactured. The light irradiation device 18 was the same as the three-dimensional modeling device 1 except that a light emitting diode manufactured by CCS (model number: LDL2-266X30GR, wavelength: 525 nm, light emission intensity: 67 mW / cm ^{2) was used.}

(Manufacturing of 3D modeling apparatus 3: Example 3)
As the three-dimensional modeling apparatus 3, the three-dimensional modeling apparatus 103 shown in FIG. 6 was manufactured. Same as the three-dimensional modeling device 1 except that a light emitting diode manufactured by Quantum Electronics Co., Ltd. (model number: UV-4H-365H-100 / 5C, wavelength: 365 nm, emission intensity: 2100 mW / cm ^{2) was used as the light irradiation device 19.} I made it.

(Manufacturing of 3D modeling apparatus C1: Comparative Example 1)
As the three-dimensional modeling apparatus C1, except that a light emitting diode manufactured by Quantum Electronics (model number: UV-4H-365H-100 / 5C, wavelength: 365 nm, emission intensity: 7 W / cm ² ) was used instead of the light irradiation apparatus 16. , A three-dimensional modeling device similar to the three-dimensional modeling device 1 was manufactured.

<Making a three-dimensional model>
Using the obtained three-dimensional modeling devices 1 to 3 and C1, three-dimensional model objects 1 to 3 and C1 were produced, respectively. The obtained three-dimensional models 1 to 3 and C1 are all three-dimensional models in which 200 layers of 50 mm × 50 mm × thickness 20 μm are laminated to have a total thickness of 4 mm.

<Evaluation of 3D model>
For 3D shaped objects (3D shaped objects 1 to 3 and C1) produced using each 3D modeling device, Suntest CPS + (manufactured by ATLAS Co., Ltd .; light source: 1500 W xenon air-cooled lamp, irradiance 100 klpx , Black standard temperature 42 ° C., lamp filter: B (outdoor direct light)) was irradiated with pseudo-sunlight for 8 hours, and the presence and degree of yellowing over time were visually observed and evaluated.
As a result, yellowing was confirmed in the three-dimensional model C1, whereas yellowing was not confirmed in any of the three-dimensional models 1 to 3.

The three-dimensional model C1 in which yellowing was confirmed was irradiated with a light emitting diode manufactured by CCS (model number: PJ-1505-2CA, wavelength: 470 nm, emission intensity: 67 mW / cm ² ) for 4 hours. The yellowing on the outer peripheral surface of the three-dimensional model C1 disappeared, but the yellowing inside did not disappear completely.

From the above results, in the three-dimensional modeling apparatus (three-dimensional modeling apparatus 1 to 3) of the example, the yellowing over time was suppressed as compared with the three-dimensional modeling apparatus (three-dimensional modeling apparatus C1) of the comparative example. It can be seen that the original model can be obtained.

10, 11, 13 Modeling unit 12 3D modeling material Discharge head 14 Support material Discharge head 16, 18, 19 Light irradiation device 20 Modeling table 30 3D modeling material cartridge 30A 3D modeling material 32 Support material cartridge 32A Support material 101, 102, 103 3D modeling equipment

Claims (14)

A discharge unit that accommodates a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator and discharges the three-dimensional modeling material.
A first visible light irradiation unit that irradiates the discharged three-dimensional modeling material with visible light having a wavelength of 400 nm or more and 430 nm or less.
A second visible light irradiation unit that irradiates the three-dimensional modeling material with visible light having a wavelength of 500 nm or more after the visible light is irradiated by the first visible light irradiation unit.
A three-dimensional modeling device equipped with. The first visible light irradiation unit is a light irradiation unit that irradiates visible light having a wavelength of 403 nm or more and 428 nm or less, and the second visible light irradiation unit irradiates visible light having a wavelength of 500 nm or more and 580 nm or less. The three-dimensional modeling apparatus according to claim 1 , which is a light irradiation unit. A discharge unit that accommodates a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator and discharges the three-dimensional modeling material.
An ultraviolet light irradiation unit that irradiates the discharged three-dimensional modeling material with ultraviolet light having a wavelength of less than 400 nm, and an ultraviolet light irradiation unit .
A first visible light irradiation unit that irradiates the three-dimensional modeling material with visible light having a wavelength of 400 nm or more and 430 nm or less after being irradiated with ultraviolet light by the ultraviolet light irradiation unit.
A three-dimensional modeling device equipped with. The first visible light irradiation unit is a light irradiation unit that irradiates visible light having a wavelength of 403 nm or more and 428 nm or less, and the ultraviolet light irradiation unit is a light irradiation unit that irradiates ultraviolet light having a wavelength of 360 nm or more and 390 nm or less. The three-dimensional modeling apparatus according to claim 3. Claims 1 to claim that the acylphosphine oxide-based photopolymerization initiator contains at least one of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Item 3. The three-dimensional modeling apparatus according to any one of Item 4. The three-dimensional modeling apparatus according to claim 5 , wherein the content of the acylphosphine oxide-based photopolymerization initiator in the entire three-dimensional modeling material is 2% by mass or more and 4% by mass or less. The three-dimensional modeling apparatus according to any one of claims 1 to 6 , wherein the three-dimensional modeling material is colorless and transparent or white. A discharge process for discharging a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator, and
A first visible light irradiation step of irradiating the three-dimensional modeling material discharged in the discharge step with visible light having a wavelength of 400 nm or more and 430 nm or less.
A second visible light irradiation step of irradiating the three-dimensional modeling material with visible light having a wavelength of 500 nm or more after the visible light is irradiated in the first visible light irradiation step.
A method for manufacturing a three-dimensional model having. The visible light emitted in the first visible light irradiation step is visible light having a wavelength of 403 nm or more and 428 nm or less, and the visible light irradiated in the second visible light irradiation step is visible light having a wavelength of 500 nm or more and 580 nm or less. The method for manufacturing a three-dimensional model according to claim 8 , which is light. A discharge process for discharging a three-dimensional modeling material containing a photopolymerizable compound and an acylphosphine oxide-based photopolymerization initiator, and
An ultraviolet light irradiation step of irradiating the three-dimensional modeling material discharged in the discharge step with ultraviolet light having a wavelength of less than 400 nm ,
The first visible light irradiation step of irradiating the three-dimensional modeling material with visible light having a wavelength of 400 nm or more and 430 nm or less after the ultraviolet light is irradiated in the ultraviolet light irradiation step.
A method for manufacturing a three-dimensional model having. The first visible light irradiation step is a step of irradiating visible light having a wavelength of 403 nm or more and 428 nm or less, and the ultraviolet light irradiation step is a step of irradiating ultraviolet light having a wavelength of 360 nm or more and 390 nm or less. 10. The method for manufacturing a three-dimensional model according to 10. Claim 8 to claim that the acylphosphine oxide-based photopolymerization initiator contains at least one of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Item 3. The method for producing a three-dimensional model according to any one of Item 11. The method for producing a three-dimensional model according to claim 12 , wherein the content of the acylphosphine oxide-based photopolymerization initiator in the entire three-dimensional model is 2% by mass or more and 4% by mass or less. The method for producing a three-dimensional model according to any one of claims 8 to 13 , wherein the three-dimensional model is colorless and transparent or white.

Images