JPH05212804A - Manufacture of teree-dimensional model - Google Patents

Abstract

PURPOSE:To ensure that an internal structure can be clearly distinguished from the exterior by adding a coloring agent to one of more than two types of photocurable blended resin containing photopolymerization initiators with different absorption wavelengths, and selectively emitting light of a common absorption wavelength to the photopolymerization initiator and the coloring agent added to the photocurable resin for curing and coloring processes. CONSTITUTION:If a blended resin is to be selectively cured and colored such a blended resin is used that its ingredients are two different types of resin, that is, a photocationic polymerization resin A' and a photoradical polymerization resin B' which contain photopolymerization initiators A, B having different spectroscopic sensitivities respeotively. The part irradiated with light of a wavelength lambda1 of each resin A', B' containing the photopolymerization initiators A, B has only the resin A' cured due to a cationio polymerization reaction. On the other hand, the part irradiated with light of wavelength lambda2 has both resins A', B' cared due to a radical and cationic polymerization reaction. In this case, a photoradical polymerization resin containing a coloring agent which becomes colored by emission of light having a specific wavelength is used as the resin B'. Thus only the irradiated part of the resin B' becomes colored by appropriately selective emission of the wavelength lambda2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a three-dimensional model, and more particularly to a method for manufacturing a three-dimensional model which allows the internal structure to be clearly seen.

[0002]

2. Description of the Related Art Conventionally, an ultraviolet laser oscillator, an optical system for guiding a laser beam output from the laser to a photocurable resin, and a three-dimensional CAD (Comput) have been used for manufacturing a three-dimensional model.
A three-dimensional three-dimensional model manufacturing apparatus has been used, which comprises a computer control unit that moves a curing unit by exposing a two-dimensional image based on erAided Design data onto the photocurable resin by laser exposure.

Since the three-dimensional model manufactured by the above apparatus is semi-transparent, not only the appearance but also the internal structure is visualized as compared with other three-dimensional models made of clay or wood.

[0004]

However, since the above-mentioned conventional three-dimensional model is semi-transparent but has a single color, especially when the internal structure of the three-dimensional model is complicated,
Alternatively, when it is necessary to accurately grasp the internal state, there is a drawback that the shape and the like cannot be identified from the outside, and a prompt solution to such a problem has been desired.

[0005]

Means for Solving the Problems The present inventor has conducted extensive studies in view of the above-mentioned circumstances, and as a result, the three-dimensional structure capable of identifying the internal structure by imparting to the resin a function capable of being selectively cured and colored by the light irradiation wavelength. The inventors have found that a model can be obtained and completed the present invention.

That is, according to the present invention, at least one of two or more photocurable mixed resins each containing a photopolymerization initiator having a different absorption wavelength contains a colorant, and the photopolymerizable resin contained in the photopolymerizable resin contains a colorant. It is intended to provide a method for producing a three-dimensional model characterized by selectively irradiating the resin with light having an absorption wavelength common to an initiator and a colorant to cure and color the resin.

The present invention further uses, as two or more photocurable mixed resins each containing a photopolymerization initiator having a different absorption wavelength, at least one resin which is colored or discolored upon curing, and the resin is contained. Provided is a method for producing a three-dimensional model, which comprises selectively irradiating the resin with light having an absorption wavelength of a photopolymerization initiator to cure and color or discolor the resin.

At least one of the mixed resins used in the present invention has a property of being cured by light irradiation, and
The light irradiation part has a function of selectively coloring or changing the resin color before irradiation to another color depending on its wavelength.

To enable the resin used in the present invention to be colored or discolored at the same time when the resin is photocured, a colorant shown in the following (a) and (b) may be added to the photocurable resin, Alternatively, the resin itself may be provided with a coloring or discoloring function as shown in (c) below.

Here, the colorant has a function of coloring by irradiation with light of a specific wavelength or foaming to make the resin cloudy. For example, (a) photo-denitrification (nitrogen foaming) compounds such as naphthoquinone diazide, acetylacetone diazide, acetylacetic acid sulfonic acid diazide (b) photochromism compounds such as spirolane dihydroindolizine.

The resin itself having a coloring or discoloring function may be, for example, (c) a resin which becomes cloudy during photocuring, such as epoxy acrylate, urethane acrylate, vinylpyrrolidone, etc., dicyclopentenyl ethyl acrylate, and photopolymerization. The thing which added the initiator is mentioned.

The method of selectively curing and coloring the mixed resin of the present invention includes photopolymerization initiators having different spectral sensitivities and resins having different polymerization types, for example, photopolymerization initiation having the spectral sensitivity as shown in FIG. A mixed resin composed of two kinds of a photo-cationic polymerization type resin A ′ and a photo-radical polymerization type resin B ′ each containing the agent (A, B) may be used. That is,
With the photopolymerization initiators A and B contained in each of the above resins, only the cationic polymerization takes place at the portion irradiated with the light having the wavelength λ ₁ and only the resin A ′ is cured, and the light having the wavelength λ ₂ is irradiated. In the portion where both radical polymerization and cationic polymerization occur, the resins A'and B'are both cured.

At this time, a photo-radical polymerization resin having a coloring function imparted by any one of the means (a), (b) and (c) is used as the resin B ', and a wavelength λ ₂ causes a coloring reaction. By appropriately selecting and irradiating with light within a possible range, only the irradiated portion of the resin B'can be colored. Further, the spectral sensitivity of the polymerization initiator and the spectral sensitivity of the colorant obtained by adding the colorant (a) or (b) to the photoradical polymerization resin or the photocationic polymerization resin If a difference is provided between them, the resin can be selectively colored.

For example, as shown in FIG. 2, which shows the relationship between the wavelengths of the photopolymerization initiator A or B and the colorant C with respect to the wavelength,
If there is a difference in the respective spectral sensitivities, only the photopolymerization initiator in the spectral sensitivity region λ ₁ where light irradiation is applied does not cause coloration or discoloration, but only the photopolymerization initiator and the colorant. The light-irradiated portion of the region λ ₂ where the spectral sensitivities of the _two overlap, is cured and colored or discolored.

As described above, by selecting and combining photopolymerization initiators and colorants having different spectral sensitivities or resins having a coloring or discoloring function and appropriately selecting the light irradiation wavelength, the resins can be color-coded into a plurality of colors. It will be possible. The obtained three-dimensional model may be post-cured by light or heat, if necessary.

As the cationic photopolymerization resin used in the present invention, for example, a novolac type epoxy compound or an alicyclic epoxy compound can be used. Examples of commercially available novolac type epoxy compounds include EO manufactured by Nippon Kayaku Co., Ltd.
CN-102S, 103, 104S, 1020, 102
7, Epikale 180S7 manufactured by Yuka Shell Epoxy Co., Ltd.
5 and the like. Examples of commercially available alicyclic epoxy compounds include CY-175 and 177 manufactured by Ciba Geigy.
179, U.S.S. C. C. Company ERL-4234, 429
9, 4221, 4206 and the like.

As the radical photopolymerization resin used in the present invention, for example, an acrylate or methacrylate compound or a spiro acetal and a spiral compound having an acryl group or a methacryl group can be used. Examples of commercially available acrylate or methacrylate compounds include Aronix M5700 and M610 manufactured by Toa Gosei Co., Ltd.
0, M8030, M152, M205, M215, M3
15, M325, M400, M405, M7200, NK ester ABPE-4, U-4H manufactured by Shin Nakamura Chemical Co., Ltd.
A, CB-1, CBX-1, Kayarad R6 manufactured by Nippon Kayaku Co., Ltd.
04, DPCA-30, DPCA-60, Kayamer PM
-1, PM-2, Sannobuco Photomer 4061,
5007, Showa Polymer Co., Ltd. Lipoxy VR60, VR9
0, SP1509, viscoat 540 manufactured by Osaka Organic Co., and the like. Examples of commercially available products of the spiro acetal and the spiral compound having an acrylic group or a methacrylic group include, for example, Showa High Polymer Co., Ltd. Spyrac E-4000X, U30.
00 etc. are mentioned.

As the photoradical polymerization initiator used in the present invention, for example, a benzophenone compound can be used. Examples of commercially available products of the compound include Irgacure 184, 651, 907 manufactured by Ciba-Geigy, and Darocur 1173, 1116, 2959 manufactured by Merck. As the photocationic polymerization initiator used in the present invention, for example, a metallocene compound, a sulfonium salt or the like can be used. Examples of commercially available metallocene compounds include Irgacure 261 manufactured by Ciba-Geigy.
Examples of commercially available sulfonium salts include Optomer SP-100 and SP-170 manufactured by Asahi Denka Co., Ltd.

The light source for exposing the resin may be any one capable of selecting a wavelength capable of curing and coloring or discoloring the resin, and examples thereof include laser light and parallel light from a high pressure mercury lamp. However, the light source of the three-dimensional model manufacturing apparatus needs to be able to arbitrarily select at least the wavelength of the light corresponding to the selected wavelength from the control unit, and for example, the selection of the wavelength by a dye laser or multiple laser oscillators, the high pressure mercury lamp light It is necessary to be able to select wavelengths by switching filters. When using parallel light from a high-pressure mercury lamp as a light source, it is necessary to use a mask, a shutter, or the like for two-dimensional patterning exposure of the photocurable resin.

[0020]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 A photocurable resin obtained by mixing a photoradical polymerization type resin and a photocationic polymerization type resin in a weight ratio of 1: 1 was used. The composition of the photo-radical polymerization resin is 40 parts by weight of epoxy acrylate (viscote 540 manufactured by Osaka Organic Co., Ltd.), 30 parts by weight of urethane acrylate, 10 parts by weight of vinylpyrrolidone, 10 parts by weight of dicyclopentenylethyl acrylate, a photopolymerization initiator (Ciba Geigy). Irgacure-369) 10 parts by weight. However, urethane acrylate has the following structure. HEA-TDI-PPG-TDI-HEA Note) HEA; hydroxyethyl acrylate TDI; 2,4-tolylene diisocyanate PPG; polypropylene glycol molecular weight 4000 In addition, the photo-radical polymerization system resin has a function which hardens and becomes cloudy. In addition, the composition of the photo-cationic polymerization resin is an alicyclic epoxy resin (Aravadite CY manufactured by Ciba-Geigy).
179) 70 parts by weight and 10 parts by weight of a photopolymerization initiator (Irgacure-261 manufactured by Ciba-Geigy). The spectral sensitivities of the cationic photopolymerization initiator and the radical polymerization initiator have the characteristics shown in FIGS. 3 and 4, respectively. An outline of the modeled device is shown in FIG. Modeling is performed by using a conventional three-dimensional stereo model manufacturing apparatus with two wavelengths (368
nm, 514 nm) was used to manufacture a three-dimensional model 61 shown in FIG. 6 designed by CAD using a device capable of selecting an Ar laser. The block portion 62 in FIG. 6 is exposed by an Ar laser (368 nm) in a region where the spectral sensitivities of the cationic polymerization initiator and the photoradical polymerization initiator overlap, and the other portions are exposed in the spectral sensitivity region of the cationic polymerization initiator only. It was exposed with a laser (514 nm). As a result, as shown in FIG. 7, a three-dimensional model was obtained in which the portion 72 exposed and cured with Ar laser (368 nm) was colored white, and the other portion 71 was semitransparent.

Example 2 70 parts by weight of an alicyclic epoxy resin (Araldite CY 179 manufactured by Ciba-Geigy) as a photo-curable resin, and a photopolymerization initiator (Irgacure-261 manufactured by Ciba-Geigy) 10
A cationic photopolymerization resin comprising 10 parts by weight of sodium o-naphthoquinonediazide-5-sulfonate and 10 parts by weight of diethylene glycol dimethyl ether as a coloring agent (nitrogen blowing agent) was used. The spectral sensitivity characteristics of the cationic photopolymerization initiator and the colorant have the characteristics shown in FIGS. 3 and 8, respectively. For modeling, the three-dimensional solid model manufacturing apparatus used in Example 1 was used to manufacture a solid model 91 shown in FIG. 9 designed by CAD. Figure 9
The inner block portion 92 is exposed by an Ar laser (368 nm) in the region where the spectral sensitivity of the photocationic polymerization agent and the colorant overlap, and the other part is exposed by the Ar laser (514 nm) in the spectral sensitivity region of only the photocationic polymerization initiator. Exposed. As a result, as shown in FIG. 10, the portion 12 exposed and cured by the Ar laser (368 nm) was foamed and colored white, and the other portion 1
1 was a red translucent solid model.

[0023]

According to the present invention, when the three-dimensional model is cured, a part or all of the three-dimensional model can be arbitrarily colored or discolored. Further, even those having a complicated internal structure can be clearly identified from the outside.

[Brief description of drawings]

FIG. 1 is a diagram showing examples of spectral sensitivity of a photocationic polymerization initiator (A) and a photoradical polymerization initiator (B).

FIG. 2 is a diagram showing examples of respective spectral sensitivities of a photopolymerization initiator (A or B) and a colorant C.

FIG. 3 is a graph showing the spectral sensitivity of the photocationic polymerization initiators used in Examples 1 and 2.

FIG. 4 is a diagram showing a molecular extinction coefficient with respect to a wavelength of a photo-radical polymerization initiator used in Example 1.

5 is a diagram showing an outline of an apparatus used in Example 1. FIG.

FIG. 6 is a perspective view showing a three-dimensional model designed by CAD according to the first embodiment.

7 is a perspective view showing a stereo model obtained in Example 1. FIG.

8 is a diagram showing the spectral sensitivity of the colorant used in Example 2. FIG.

FIG. 9 is a perspective view showing a three-dimensional model designed by CAD in Example 2.

10 is a perspective view showing a stereo model obtained in Example 2. FIG.

[Explanation of symbols]

 A. …… Photo-cationic polymerization initiator B. ...... Photo radical polymerization initiator C. …… Colorant 51 …… CAD data 52 …… Controller 53 …… Ar laser (368 nm) 54 …… Ar laser (514 nm) 55 …… Mirror 56 …… Photocurable resin 61 …… Three-dimensional model 62 …… Block part 71 ... Translucent part 72 ... Coloring part 91 ... Solid model 92 ... Block part 11 ... Red translucent part 12 ... Coloring part

Claims (2)

[Claims] 1. A coloring agent is contained in at least one of two or more photo-curable mixed resins each containing a photo-polymerization initiator having a different absorption wavelength, and the photo-polymerization initiator and the coloring are contained in the photo-curable resin. A method for producing a three-dimensional model, which comprises selectively irradiating the resin with light having an absorption wavelength common to that of the agent to cure and color the resin. 2. A photopolymerization initiator contained in at least one resin which is colored or discolored upon curing as two or more photocurable mixed resins each containing a photopolymerization initiator having a different absorption wavelength. A method for producing a three-dimensional model, which comprises selectively irradiating the resin with light having an absorption wavelength of to cure and color or discolor the resin.