JP2014000820A - Optical three-dimensionally shaped article having low yellowness index - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a three-dimensionally shaped article low in discoloration such as yellowing.SOLUTION: The optical three-dimensionally shaped article manufactured using a photocurable resin composition is irradiated with light having a wavelength within a range of 430-500 nm so that the total irradiation intensity of the light of the wavelength of 430-500 nm at the surface of the optical three-dimensionally shaped article is 15 W/mor more. The radiated light does not include light of a wavelength of 400 nm or less.

Description

The present invention relates to an optical three-dimensional structure having a low yellowness. By processing the optical three-dimensional modeled object obtained by performing the optical three-dimensional modeling using the photocurable resin composition using the method and apparatus described in the present specification, the mechanical characteristics of the optical three-dimensional modeled object are obtained. In addition, the optical three-dimensional object of the present invention having a low yellowness can be obtained in a short time while maintaining good physical properties and other properties.

In recent years, an optical three-dimensional modeling method and apparatus for manufacturing a three-dimensional model by photocuring a photocurable resin composition based on data input to a three-dimensional CAD have been put into practical use.
In this optical three-dimensional modeling technology, a cured resin layer having a predetermined shape pattern by selectively irradiating a modeling surface made of a photocurable resin composition with computer-controlled light and photocuring to a predetermined thickness And forming a modeling surface on the cured resin layer by further applying a photocurable resin composition for one layer, and selectively irradiating the modeling surface with light controlled by a computer. In general, a method of repeating a modeling operation of forming a cured resin layer having a predetermined shape pattern by photocuring to a thickness many times until a three-dimensional modeled object having a predetermined size and shape is obtained is widely adopted.

  The three-dimensional object obtained by the above-mentioned optical three-dimensional modeling technology is a model for verifying the appearance design of various industrial products in the middle of design, a model for checking the functionality of parts, and a resin for producing molds. It is widely used as a base model for making molds and molds. In recent years, it is also used for art and crafts such as restoration of artworks, imitation and contemporary art, and design presentation models for glass-walled buildings. It is supposed to be.

With the expansion of applications of optical three-dimensional objects, optical three-dimensional objects that are free of discoloration such as yellowing and have excellent colorless transparency, and optical three-dimensional objects that are manufactured using colorants such as dyes and pigments However, there is a demand for an optical three-dimensional modeled object that is not deteriorated in color tone due to discoloration or the like, and is colored in the original good color tone of the colorant.
However, many of the conventional optical three-dimensional objects are somewhat discolored, such as yellowing, and are inferior in colorless transparency, or those using a colorant may deteriorate in color due to discoloration, such as yellowing. It was happening.
Although the cause of discoloration such as yellowing and poor color tone in the optical three-dimensional model has not yet been fully elucidated, the radical polymerizable organic compound, the cationic polymerizable organic compound contained in the photocurable resin composition, Compounds such as light-sensitive radical polymerization initiators and light-sensitive cationic polymerization initiators, and resin components generated by photocuring become chemically unstable when irradiated with light (particularly ultraviolet rays) during optical three-dimensional modeling. As a result of the alteration, it is presumed that structural parts and components having a chromophore / auxiliary chromophore such as a conjugated double bond are generated in the optical three-dimensional structure.

  For the purpose of providing an optical three-dimensional structure that has little discoloration such as yellowing and is excellent in transparency, an epoxy compound in which the content of an epoxy compound of glycidyl type is less than 0 to 30% by weight, does not contain a hydroxyl group, or A photocurable resin composition containing a polyfunctional (meth) acrylate having a low hydroxyl group content, a polyether polyol compound, a cationic polymerization initiator, and a radical polymerization initiator has been proposed (see Patent Document 1). However, it is difficult to say that the optical three-dimensional model obtained from the photocurable resin composition is sufficiently excellent in terms of colorless transparency. Moreover, in this photocurable resin composition, since it is necessary to use a combination of specific components, the composition design of the curable resin composition and the physical properties (mechanical characteristics, dimensional stability) of the resulting three-dimensional model Dimensional accuracy, heat resistance, and the like), and it is not always possible to manufacture a three-dimensional molded article having specific mechanical characteristics, modeling accuracy, dimensional accuracy, heat resistance, and the like.

In addition, for the purpose of obtaining a three-dimensional shaped product with little yellowing in a high temperature environment, (A) diphenyl (phenylthiophenyl) sulfonium-based cationic polymerization initiator, (B) phenol-based antioxidant, (C) cationic polymerization Compound (D) radical polymerization initiator, (E) radical polymerizable compound, (F) 2-mercaptobenzothiazole, 2- (4-morpholinodithio) benzothiazole, diisopropylxanthogen disulfide and diphenyl disulfide There has been proposed a resin composition for optical three-dimensional modeling containing one or more selected compounds and (G) a polyether polyol compound (see Patent Document 2).
However, this Patent Document 2 only shows the difference between the yellowness (yellow index) of a three-dimensional structure immediately after stereolithography and the yellowness after heating the three-dimensional structure at 80 ° C. for 2 hours. Yes, there is no description on the color tone (for example, yellowness) of the three-dimensional model itself before heating obtained by optical modeling, and therefore the color tone of the three-dimensional model itself obtained by optical modeling is poor. There is no disclosure about how to improve the color tone in some cases.
Moreover, in the invention of Patent Document 2, since it is necessary to prepare the resin composition for optical three-dimensional modeling in combination with the specific components (A) to (G), the resin composition for optical three-dimensional modeling is also used. There are significant restrictions on the blending design of the objects and the physical properties of the resulting three-dimensional model.
Further, yellowing is prevented by reducing the irradiation energy by reducing the lamination thickness at the time of modeling, lowering the laser output and / or increasing the scanning speed. However, if the lamination thickness is reduced, not only will the modeling time increase because the number of layers of the model increases, but the risk of modeling failure increases because the tolerance for non-uniform layer thickness caused by surface tension and bubbles decreases. . In addition, when the irradiation energy is reduced, the degree of cure of the model decreases and becomes soft, so that the mechanical strength of the model decreases, and the interlaminar adhesion decreases and delamination easily occurs. There was a drawback that it was easy to do.

Furthermore, in order to conceal discoloration such as yellowing of the optical three-dimensional modeled object obtained by optical modeling, the use of fluorescent whitening agents and dyes is also performed.
However, since the fluorescent brightening agent generally has absorption in the ultraviolet part, when blended in the photocurable resin composition, it causes a decrease in the energy of ultraviolet rays irradiated to the photocurable resin composition during optical modeling, The photocuring resin composition has a decrease in photocuring sensitivity and a variation in cured thickness, and it tends to be difficult to produce an optical three-dimensional model having excellent physical properties.
Also, the dye, like the fluorescent brightening agent, may reduce the photocuring sensitivity of the photocurable resin composition, and may cause an undesirable discoloration due to a change over time, and it is desired to be colored lightly. In some cases, discoloration such as yellowing cannot be completely hidden.
In addition, although it has been known that when a model is left for a long period of time, decolorization proceeds and becomes colorless or yellows, the cause is not clear, and even when it is decolored, it takes several days or more. It was necessary. Optical three-dimensional modeling is one of the techniques called rapid prototyping, and it is required to create a model within a few hours to a day and use it immediately. That lacks practicality.

  From the above points, if the optical three-dimensional object obtained by stereolithography has a discoloration such as yellowing, it is inferior in colorless transparency, or the color tone is poor, the dynamics of the optical three-dimensional object That can easily and quickly eliminate or reduce discoloration such as yellowing of optical three-dimensional objects while maintaining good physical properties and other physical properties, and is excellent in colorless transparency or using a colorant Therefore, there is a demand for a technique that can produce an optical three-dimensional object having an excellent color tone inherent to the colorant.

Special table 2007-516318 Japanese Patent No. 3930888

Paul F. Jacobs, “Rapid Prototyping & Manufacturing, Fundamentals of Stereo-Lithography”, “Society of Manufacturing Engineers”, 1992, p. 28-39.

The purpose of the present invention is to obtain mechanical properties of an optical three-dimensional model and other when discoloration such as yellowing occurs in an optical three-dimensional model obtained by optical modeling using a photocurable resin composition. While maintaining good physical properties, discoloration such as yellowing can be quickly eliminated or reduced in a short time with a simple operation, excellent in colorless transparency, or in the case of using a colorant The present invention provides an optical three-dimensional object that can be converted into an optical three-dimensional object having an excellent color tone and an apparatus therefor, and an optical three-dimensional object that has a low yellowness .

In order to achieve the above object, the present inventors have conducted intensive studies. As a result, when discoloration such as yellowing occurs in the optical three-dimensional modeled object obtained by performing the optical three-dimensional modeling using the photocurable resin composition, 430 with respect to the optical three-dimensional modeled object The total irradiation intensity of light having a wavelength within a range of ˜500 nm (blue light) and having a wavelength of 400 nm or less, particularly light that does not contain ultraviolet light, has a specific value. When irradiated in this way, while maintaining the original mechanical properties and other physical properties of the optical three-dimensional model, it is possible to quickly eliminate or reduce the discoloration such as yellowing in a short time, and is it excellent in colorless transparency? In addition, it has been found that an optical three-dimensionally shaped article exhibiting the color tone inherent to the colorant can be obtained by using the colorant.
And the present inventors described above that the color tone of the optical three-dimensional object is improved by irradiating light having a wavelength of 400 nm or less, in particular, ultraviolet light, and light having a wavelength of 430 to 500 nm (blue light). The processing method includes an optical three-dimensional object that has been subjected to post-curing treatment by irradiation with ultraviolet light and / or heating after optical three-dimensional modeling, and no post-curing treatment by ultraviolet irradiation and / or heating after optical three-dimensional modeling. It was found to be effective for both optical three-dimensional objects.

Moreover, the present inventors implement the said method for improving the color tone of an optical three-dimensional model | mold with respect to the three-dimensional model | molding object which irradiated the ultraviolet-ray to the three-dimensional model | molded object obtained by optical modeling, and was postcured. In the case of
A post-processing device including a light source (A) that emits light including ultraviolet light and a light source (B) that emits light that includes light having a wavelength in the range of 430 to 500 nm and does not include light having a wavelength of 400 nm or less. The optical three-dimensional model is obtained by irradiating light from the light source (A) to the optical three-dimensional model obtained by performing optical three-dimensional modeling using the photocurable resin composition, and post-curing the optical three-dimensional model with ultraviolet rays. And then irradiating the light from the light source (B) so that the total irradiation intensity of the light having a wavelength of 430 to 500 nm on the surface of the optical three-dimensional model becomes a specific value;
-Obtained by using an aftertreatment device equipped with a light source (C) that emits light including ultraviolet light and light having a wavelength in the range of 430 to 500 nm, and performing optical three-dimensional modeling using the photocurable resin composition. The optical three-dimensional object is irradiated with light from the light source (C) and the optical three-dimensional object is post-cured with ultraviolet rays contained in the light emitted from the light source (C), and then from the light source (C). A method of irradiating light having a wavelength of 400 nm or less from emitted light, in particular, light excluding ultraviolet rays 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 has a specific value ;
And the like.

  Furthermore, the inventors have found that the above-described method for improving the color tone of the optical three-dimensional object found by the inventors is a photocurable resin composition containing a radical polymerizable organic compound and a photosensitive radical polymerization initiator. Obtained using an optical three-dimensional structure obtained by using a photopolymerizable resin composition containing a radical polymerizable organic compound, a photosensitive radical polymerization initiator, a cationic polymerizable organic compound, and a photosensitive cationic polymerization initiator The present invention has been found to be effective for any of the optical three-dimensional objects to be produced, and the present invention has been completed based on these various findings.

That is, the present invention
(1) An optical three-dimensional structure manufactured using a photocurable resin composition, and the spectral transmittance obtained by measuring with a spectrophotometer is numerically calculated by a method defined in JIS-K7373, This is an optical three-dimensional object having a yellowness of 2.4 or less at a thickness of 5 mm obtained under the conditions of auxiliary illuminant C and visual field of 2 °.
Here, the detailed method for obtaining the yellowness is as described in the section of Examples below.
And this invention,
(2) An optical three-dimensional object obtained by performing optical three-dimensional modeling using a photocurable resin composition is irradiated with light having a wavelength in the range of 430 to 500 nm on the surface of the optical three-dimensional object. (3) the optical three-dimensional object obtained by irradiation treatment so that the total irradiation intensity of light having a wavelength of 430 to 500 nm is 15 W / m ² or more; and
(3) The optical three-dimensional structure according to (2), wherein the light having a wavelength in the range of 430 to 500 nm is light that does not include light having a wavelength of 400 nm or less.

In the above (2) and / or (3), the optical three-dimensional object to be irradiated with light having a wavelength in the range of 430 to 500 nm is post-cured by performing ultraviolet irradiation and / or heating after the optical three-dimensional modeling. even stereolithography product was subjected to a treatment, or a stereolithography product not subjected to post-curing treatment by irradiation and / or heating of the ultraviolet ray after stereolithography.
In the above (3), the light used for the processing of the optical three-dimensional structure is emitted from a light source that emits light that includes light having a wavelength in the range of 430 to 500 nm and does not include light having a wavelength of 400 nm or less. It is light obtained by removing light having a wavelength of 400 nm or less from light emitted from a light source that emits light including light having a wavelength in the range of 430 to 500 nm and light having a wavelength of 400 nm or less.
Further, the optical three-dimensional object of the present invention includes a light source (A) that emits light including ultraviolet light, and light that includes light having a wavelength in the range of 430 to 500 nm and does not include light having a wavelength of 400 nm or less. The light from the light source (A) is irradiated to an optical three-dimensional object obtained by performing an optical three-dimensional object using a photocurable resin composition using a post-processing device provided with a radiating light source (B). After the optical three-dimensional model is post-cured with ultraviolet light, the light from the light source (B) has a total irradiation intensity of 15 W / m ² or more at a wavelength of 430 to 500 nm on the surface of the optical three-dimensional model. It can obtain by irradiating.
The optical three-dimensional object of the present invention removes ultraviolet rays from a light source (C) that emits light including ultraviolet rays and light having a wavelength in the range of 430 to 500 nm, and light emitted from the light source (C). Emitted from a light source (C) to an optical three-dimensional object obtained by performing an optical three-dimensional object model using a photocurable resin composition using a post-processing apparatus equipped with an ultraviolet ray cutting means (D) After the optical three-dimensional object is post-cured with ultraviolet rays contained in the light emitted from the light source (C), the wavelength is changed by the ultraviolet ray cutting means (D) from the light emitted from the light source (C). It can also be obtained by irradiating the light excluding light of 400 nm or less so that the total irradiation intensity of light having a wavelength of 430 to 500 nm on the surface of the optical three-dimensional model becomes 15 W / m ² or more.

Then, the process described above is irradiated with light and the wavelength comprises light having a wavelength in the range of 430~500nm does not include the following light 400nm in stereolithography object, eliminating the discoloration of optical three-dimensional object or Can be reduced.
Optics obtained by using a photocurable resin composition containing a radical polymerizable organic compound, a photosensitive radical polymerization initiator, a cationic polymerizable organic compound and a photosensitive cationic polymerization initiator as the optical three-dimensional structure of the present invention A three-dimensional modeled object can be mentioned.

Further, the optical three-dimensional object of the present invention having a low yellowness includes a light source (A) that emits light including ultraviolet light, and light having a wavelength in the range of 430 to 500 nm and light having a wavelength of 400 nm or less. It can manufacture using a processing apparatus provided with the light source (B) which radiates | emits the light which does not contain.
Furthermore, the optical three-dimensional structure of the present invention with low yellowness includes a light source (C) that emits light including ultraviolet light and light having a wavelength in the range of 430 to 500 nm, and light emitted from the light source (C). Can be manufactured using a processing apparatus provided with ultraviolet cut means (D) that removes light having a wavelength of 400 nm or less.

By processing an optical three-dimensional object that has undergone discoloration such as yellowing by the above-described method, the optical three-dimensional object is maintained while maintaining the mechanical properties and other physical properties that the optical three-dimensional object originally has. Discoloration such as yellowing that has occurred in products can be easily or quickly eliminated or reduced in a short time, and it is excellent in colorless transparency, or in the case of using a colorant, it exhibits an excellent color tone inherent to the colorant. It can be changed to an optical three-dimensional model.
The above-described processing methods include an optical three-dimensional object that has been subjected to post-curing treatment by irradiation with ultraviolet light and / or heating after optical three-dimensional modeling, and a post-curing treatment by ultraviolet irradiation and / or heating after optical three-dimensional modeling. This is effective for both optical three-dimensional objects that are not applied.
The treatment method described above includes an optical three-dimensional structure obtained using a photocurable resin composition containing a radical polymerizable organic compound and a photosensitive radical polymerization initiator, and a radical polymerizable organic compound, photosensitive radical polymerization initiation. It can be effectively carried out for any of the optical three-dimensional objects obtained by using a photocurable resin composition containing an agent, a cationically polymerizable organic compound and a photosensitive cationic polymerization initiator.

The present invention is described in detail below.
In the present invention, the optical three-dimensional structure obtained by performing the optical three-dimensional modeling using the photocurable resin composition includes “light having a wavelength within a range of 430 to 500 nm and having a wavelength of 400 nm or less. The process is performed by irradiating with “light that does not contain” [hereinafter sometimes referred to as “light (α)”].
The light (α) used in the present invention is not particularly limited as long as it is “light including light having a wavelength in the range of 430 to 500 nm and not including light (particularly ultraviolet light) having a wavelength of 400 nm or less”.

The light having a wavelength of 430 to 500 nm is a visible light exhibiting a blue color. Here, according to the light (α) used in the processing of the optical three-dimensional object in the present invention, “having a wavelength within the range of 430 to 500 nm. “Including light” means that the light (α) used for the treatment of the optical three-dimensional structure includes at least light having a wavelength in the range of 430 to 500 nm (blue light having a wavelength in the range of 430 to 500 nm). Means that
The light (α) may be “light having one or more energy intensity peaks in the wavelength range of 430 to 500 nm and not including light having a wavelength of 400 nm or less” or “430 Even if it does not have a peak of light energy intensity within the wavelength range of ˜500 nm, but at least the light energy is distributed within the wavelength range of 430 to 500 nm and does not include light having a wavelength of 400 nm or less. It may be a combination of the two lights.

  The light (α) used for processing the optical three-dimensional object is “light having one or more energy intensity peaks in the wavelength range of 430 to 500 nm and not including light having a wavelength of 400 nm or less”. , The peak shape of the light energy intensity in the wavelength range of 430 to 500 nm may be either a gentle chevron shape or a sharp chevron shape. When the light (α) has two or more light energy intensity peaks in the wavelength range of 430 to 500 nm, the shape and height of each peak may be the same or different. Or either.

  In addition, the light (α) used for the processing of the optical three-dimensional object does not have a peak of light energy intensity within the wavelength range of 430 to 500 nm, but at least the light energy is distributed within the wavelength range of 430 to 500 nm. In the wavelength range of 430 to 500 nm, the light energy intensity is uniformly or almost uniformly distributed over the entire wavelength range of 430 to 500 nm. (When the horizontal axis represents the wavelength and the vertical axis represents the light energy intensity, the light energy intensity distribution is flat or nearly flat over the wavelength range of 430 to 500 nm and does not include light having a wavelength of 400 nm or less. Light) or from one to the other in the wavelength range of 430-500 nm (from 430 nm to 500 nm). It or toward the 430nm from 500 nm) and wavelengths of light energy intensity is not increased or decreased without the tapered shape may be a light that does not include the following light 400 nm. In some cases, the light (α) includes light having a valley-shaped light energy intensity distribution in which the light energy intensity is low at any wavelength point in the wavelength range of 430 to 500 nm and having a wavelength of 400 nm or less. There may be no light.

As the light (α) that can be used in the present invention, for example,
-Light having a wavelength of 430 to 500 nm (blue light) not including light having a wavelength of 400 nm or less;
-Light having a wavelength of 450 to 500 nm (blue light) not including light having a wavelength of 400 nm or less;
-Light having a wavelength exceeding 500 nm together with light in the wavelength range of 430 to 500 nm (blue light) [for example, light having a wavelength of 500 to 570 nm (green light), light having a wavelength of 530 to 590 nm (yellowish green light), wavelength Light of 570 to 590 nm (yellow light), light of wavelength 590 to 620 nm (orange light), light of wavelength 620 to 750 nm (red light) or more], and light having a wavelength of 400 nm or less Does not contain light;
White light not including light having a wavelength of 400 nm or less;
And so on.

In the present invention, an optical three-dimensional object that has undergone discoloration such as yellowing is irradiated with light (α) that includes light having a wavelength in the range of 430 to 500 nm and does not include light having a wavelength of 400 nm or less. This eliminates or reduces discoloration such as yellowing, and is excellent in colorless and transparent optical three-dimensional objects, and in optical three-dimensional objects that contain colorants, the optical three-dimensional objects that have the original excellent color tone You can get things.
The processing method of the present invention is particularly effective for improving the color tone of a yellowed optical three-dimensional object, but is not limited to a yellowed optical three-dimensional object, for example, brown, yellow orange, yellowish brown, etc. It is also effective as a method for improving the color tone of an optical three-dimensional model.

Even if the light used for the processing of the optical three-dimensional structure includes light having a wavelength in the range of 430 to 500 nm (blue light), the light having a wavelength of 400 nm or less, particularly ultraviolet light, When the optical three-dimensional object is irradiated, poor color tone such as yellowing of the optical three-dimensional object is amplified, or the bleaching speed is slowed in competition with decolorization. Therefore, the light (α) has a wavelength of 400 nm or less. It is necessary not to contain light, especially ultraviolet rays.
In addition, even if the light does not include light having a wavelength of 400 nm or less, when the optical three-dimensional object is irradiated with light that does not include light (blue light) having a wavelength in the range of 430 to 500 nm, The improvement effect of discoloration such as yellowing of a three-dimensional modeled object is small, and in some cases, poor color tone may increase. Although light having a wavelength of 400 to 430 nm may be included, since it is close to the ultraviolet region, contribution to decolorization (color tone improvement) is small.

In the present invention, in processing an optical three-dimensional object by irradiating light (α), the surface of the optical three-dimensional object to be irradiated with light (α) [that is, light (α) is directly irradiated. The three-dimensional object is irradiated with light (α) so that the total irradiation intensity of light within the wavelength range of 430 to 500 nm on the surface is 15 W / m ² or more.
If the total irradiation intensity of light within the wavelength range of 430 to 500 nm on the irradiation surface of the optical three-dimensional object is low, decolorization proceeds to some extent, but because the speed is slow, it may be due to yellowing of the optical three-dimensional object It becomes impossible to efficiently improve poor color tone in a short time.
The total irradiation intensity of light within a wavelength range of 430 to 500 nm on the irradiation surface of the optical three-dimensional object is preferably 25 W / m ² or more, more preferably 30 W / m ² or more, and 40 W / m. More preferably, it is ² or more. The upper limit of the total irradiation intensity of light within the wavelength range of 430 to 500 nm on the irradiation surface of the optical three-dimensional object is not particularly limited, but if the irradiation intensity is too high, heat from the light source or optical three-dimensional It is necessary to take measures against the temperature rise of the molded object (Note that a light source that can continuously irradiate light over a wide range such that the total irradiation intensity of light within a wavelength range of 430 to 500 nm exceeds 1000 W / m ^2. Is difficult to obtain).

Here, the total irradiation intensity of the light within the wavelength range of 430 to 500 nm on the surface irradiated with light in the optical three-dimensional structure in the present invention is determined by the following method <1> or << 2 >>. Can do.
<< 1 >> Spectral irradiation intensity P (λ) for each wavelength on the surface of an optical three-dimensional object being irradiated with light using a spectral illuminometer at the time of light irradiation treatment to the optical three-dimensional object (unit) : W / m ² · nm) is measured in the wavelength range of 430 to 500 nm, and the spectral irradiation intensity P (λ) in the wavelength range of 430 to 500 nm is integrated (totaled), and the light of the optical three-dimensional object is obtained. Method for obtaining total irradiation intensity (W / m ² ) of light within a wavelength range of 430 to 500 nm on the irradiated surface [Spectral irradiation intensity P (λ) for each wavelength in the wavelength range of 430 to 500 nm as it is When using a spectral illuminometer that can measure directly].
<< 2 >> At the time of the light irradiation treatment to the optical three-dimensional object, a irradiance meter is used, and the wavelength range of 380 to 780 nm (visible light range) on the surface irradiated with the light in the optical three-dimensional object is visible. While measuring the total light irradiation intensity Q (unit: W / m ² ) of light and using an optical spectrum analyzer, a wavelength range of 380 to 780 nm on the surface irradiated with light in the optical three-dimensional model ( obtains the relative spectral intensity curve F in the visible light region), from the relative spectral intensity curve F, the integral value L _a and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380 to 780 nm (visible light region) The integral value L _B of the relative spectral intensity of each is calculated, and the wavelength on the surface irradiated with the light of the optical three-dimensional structure is within a range of 430 to 500 nm from the formula: Q × (L _B / L _A ) Total light irradiation Method of obtaining intensity [in the case of not using a spectral illuminometer that directly measures the spectral irradiation intensity P (λ) for each wavelength in the wavelength region of 430 to 500 nm as it is].

In the present invention, the type of the light source for irradiating the optical three-dimensional object with light (α) is not particularly limited, and includes light having a wavelength in the range of 430 to 500 nm and light having a wavelength of 400 nm or less. Any light source can be used as long as the total irradiation intensity of the light within the range of 430 to 500 nm of light on the surface of the optical three-dimensional object is 15 W / m ² or more. .
As a light source that can be used to irradiate light (α) to an optical three-dimensional object, for example,
A light source that emits light having a wavelength of 430 to 500 nm without emitting light having a wavelength of 400 nm or less (preferably a blue light emitting diode);
A light source that does not emit light having a wavelength of 400 nm or less and that emits light including light having a wavelength of 430 to 500 nm [light having a wavelength of 500 nm or more together with light within a wavelength range of 430 to 500 nm, for example, a wavelength of 500 to 500 570 nm light (green light), 530 to 590 nm light (yellowish green light), 570 to 590 nm light (yellow light), 590 to 620 nm light (orange light), 620 to 750 nm light (red) A light source that emits light containing one or more of light);
A light source that emits white light not containing light having a wavelength of 400 nm or less (preferably a white light);
A light source that emits light including ultraviolet light and light having a wavelength of 430 to 500 nm (for example, a fluorescent lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, etc.) and a wavelength included in the light emitted from the light source is 400 nm UV blocking means for removing the following light (for example, a glass plate, an acrylic plate, a polycarbonate plate, a quartz plate with a UV absorbing coating or a UV absorbing film attached, and a resin composition by adding a UV absorber. A combination of a resin plate or the like produced by using a UV filter that transmits light having a wavelength of 430 to 500 nm and absorbs light having a wavelength of 400 nm or less;
And so on.

In optical three-dimensional modeling, in order to improve mechanical properties, dimensional stability, heat resistance, abrasion resistance, surface hardness, smoothness, etc., and eliminate stickiness of the surface, the three-dimensional modeling obtained by optical modeling The post-curing by applying ultraviolet irradiation and / or heat treatment is widely performed. However, an optical three-dimensional object that has been post-cured by applying ultraviolet irradiation and / or heat treatment is subjected to ultraviolet irradiation and / or heat treatment. Alternatively, the degree of discoloration such as yellowing may be larger than that of an optical three-dimensional model that has not been post-cured by heating. Moreover, even if it is an optical three-dimensional molded object which has not performed the postcure process by an ultraviolet-ray and / or a heating, the kind and composition of the used photocurable resin composition, the component contained in a photocurable resin composition Discoloration such as yellowing may occur in the optical three-dimensional modeled object depending on the type and the optical modeling conditions.
Therefore, the processing method of the present invention for irradiating light (α) to an optical three-dimensional object is an optical in which discoloration such as yellowing has occurred by post-curing treatment by irradiation with ultraviolet rays and / or heating after optical three-dimensional object formation. It can be effectively carried out on any of the three-dimensional modeled object and the optical three-dimensional modeled object that has undergone discoloration such as yellowing that has not been subjected to post-curing treatment by ultraviolet irradiation or heating.

The irradiation time of light (α) to the optical three-dimensional object is the degree of discoloration of the optical three-dimensional object, the irradiation intensity of light (α) on the surface of the optical three-dimensional object, and the size of the optical three-dimensional object , The shape, the type of resin forming the optical three-dimensional model, and the type and composition of the components contained in the photocurable resin composition used for the production of the optical three-dimensional model, In the present invention, the total irradiation intensity of light having a wavelength of 430 to 500 nm on the surface of the optical three-dimensional object is included in the light (α) including light having a wavelength in the range of 500 nm and not including light having a wavelength of 400 nm or less. When irradiating at a prescribed 15 W / m ² or more, preferably 25 W / m ² or more, more preferably 30 W / m ² or more, and even more preferably 40 W / m ² or more, usually about 30 minutes to 8 hours. In particular, irradiation for about 1 to 5 hours It is possible to greatly reduce discoloration such as yellowing of the optical three-dimensional object, and thereby, the optical three-dimensional object that is excellent in colorless transparency, and the optical three-dimensional object that uses the colorant, An optical three-dimensional model having an excellent color tone can be obtained.

  The temperature (the temperature and / or the atmospheric temperature of the optical three-dimensional modeled object) when irradiating light (α) to the optical three-dimensional modeled object is not particularly limited, but is generally an ambient temperature of 15 to 50 ° C., particularly Performing the irradiation treatment with light (α) at an ambient temperature of 20 to 40 ° C. facilitates the light (α) irradiation operation, the effect of improving the discoloration of the optical three-dimensional object, and the heat of the optical three-dimensional object. This is preferable from the viewpoint of preventing deformation.

In the case where the process of irradiating light (α) to the optical three-dimensional modeling is performed on the optical three-dimensional object that has been subjected to post-curing treatment by irradiation with ultraviolet rays and / or heating after the optical three-dimensional modeling, irradiation with ultraviolet rays In addition, the light (α) irradiation treatment may be performed separately from the post-curing treatment of the optical three-dimensional modeled object by heating, or the light (α) is followed by the ultraviolet ray irradiation and / or heating post-curing treatment. ) Irradiation treatment may be performed.
When the optical three-dimensional structure to be irradiated with light (α) is one that has been post-cured by irradiation with ultraviolet rays and / or heating after optical three-dimensional modeling, a processing method for the post-curing process The conditions and conditions can be the same methods and conditions as in the post-curing treatment conventionally employed in optical three-dimensional modeling.
Although not limited, for example, when the post-curing treatment is performed by irradiating with ultraviolet rays, light having a wavelength of 400 nm or less, preferably using ultraviolet rays having a wavelength of 340 to 380 nm, 0.5 to 10 mW / cm ² , In particular, the post-curing treatment can be performed with an energy intensity of 1 to ⁵ mW / cm ² .
Moreover, when performing a postcure process by heating, 40-180 degreeC, Preferably the heating temperature of 40-80 degreeC is employable, for example.

In the case of performing a post-curing process by irradiating an optical three-dimensional model obtained by optical three-dimensional modeling with ultraviolet rays, followed by irradiation with light (α), for example,
(1) A light source (A) that emits light including ultraviolet light and light (α) that includes light (blue light) having a wavelength in the range of 430 to 500 nm and does not include light having a wavelength of 400 nm or less. The light from the light source (A) is irradiated to an optical three-dimensional object obtained by performing an optical three-dimensional object using a photocurable resin composition using a post-processing device including both of the light sources (B). After the optical three-dimensional model is post-cured with ultraviolet light, the light (α) is emitted from the light source (B), and the total irradiation intensity of light having a wavelength of 430 to 500 nm on the surface of the optical three-dimensional model is 15 W / m ^2. A method of irradiating so that
(2) A light source (C) that emits light including ultraviolet light and light having a wavelength in the range of 430 to 500 nm (blue light), and light having a wavelength of 400 nm or less are excluded from light emitted from the light source (C) Light from the light source (C) is irradiated as it is onto an optical three-dimensional object obtained by performing an optical three-dimensional object model using a photocurable resin composition using a post-processing device equipped with an ultraviolet cut means (D). After the optical three-dimensional structure is post-cured with ultraviolet rays contained in the light emitted from the light source (C), the light having a wavelength of 400 nm or less is emitted from the light emitted from the light source (C) by an ultraviolet cut means (D A method of irradiating the light removed in the above manner so that the total irradiation intensity of the light having a wavelength of 430 to 500 nm on the surface of the optical three-dimensional object becomes 15 W / m ² or more;
Etc. can be adopted.

Examples of the light source (A) in the method (1) include a fluorescent lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, and an ultraviolet lamp. In addition, as the light source (B) in the method (1), any light source can be used as long as it does not include light having a wavelength of 400 nm or less and emits light having a wavelength of 430 to 500 nm. , White diode, blue lamp, white lamp, organic EL, and the like.
In addition, as the light source (C) in the above method (2), any light source that emits light including both ultraviolet rays and light having a wavelength of 430 to 500 nm can be used. Specific examples include the above-described fluorescent lamp, A high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, etc. can be mentioned.
Further, as the ultraviolet ray cutting means (D) in the method (2), it is possible to reliably remove light having a wavelength of 400 nm or less including ultraviolet light without blocking light having a wavelength of 430 to 500 nm. Any of the above can be used, for example, a glass plate, acrylic plate, polycarbonate plate, quartz plate coated with an ultraviolet absorbing film as described above, or a resin produced using a resin composition to which an ultraviolet absorber is added. An ultraviolet absorption filter made of a plate or the like can be used.

  As an optical three-dimensional structure to which the processing method of the present invention is applied, a photocurable resin composition is used, and light is selectively irradiated to a modeling surface made of the photocurable resin composition to have a predetermined thickness. A cured resin layer having a predetermined shape pattern is formed by photocuring, and a one-layer photocurable resin composition is formed on the cured resin layer to form a modeling surface, and light is applied to the modeling surface. An optical three-dimensional modeled object obtained by an optical modeling method that is selectively irradiated and photocured to a predetermined thickness to form a cured resin layer having a predetermined shape pattern by repeating many times, or Any optical three-dimensional object that is post-cured by irradiating ultraviolet light and / or heating the optical three-dimensional object, as long as the optical three-dimensional object has a poor color tone due to discoloration such as yellowing Good.

The optical three-dimensional structure to which the treatment of the present invention is applied comprises (a) a photocurable resin composition containing a radical polymerizable organic compound and a photosensitive radical polymerization initiator, and (b) a cationic polymerizable organic compound and a photosensitive cation. A photocurable resin composition containing a polymerization initiator, or (c) a photocurable resin composition containing a radical polymerizable organic compound, a cationic polymerizable organic compound, a photosensitive radical polymerization initiator, and a photosensitive cationic polymerization initiator It may be manufactured from any of the products. Among them, the optical three-dimensional structure includes the photocurable resin composition of (c), that is, a radical polymerizable organic compound, a cationic polymerizable organic compound, a photosensitive radical polymerization initiator, and a photosensitive cationic polymerization initiator. Because it is manufactured using a photocurable resin composition, the modeling speed when manufacturing an optical three-dimensional model is fast, and the mechanical characteristics and modeling accuracy of the optical three-dimensional model are excellent. preferable.
In the photocurable resin composition of (b) and (c), in particular, in the photocurable resin composition of (c), as a part of the cationically polymerizable organic compound contained in the photocurable resin composition, Inclusion of at least one oxetane compound selected from a monooxetane compound having one oxetane group and a polyoxetane compound having two or more oxetane groups improves the photocuring sensitivity of the photocurable resin composition and cures it. It is possible to improve the dimensional accuracy by reducing the volumetric shrinkage and improve the dimensional stability by improving the water resistance and moisture resistance.

  The radical polymerizable organic compound used in the photocurable resin compositions (a) and (c) causes a polymerization reaction and / or a cross-linking reaction when irradiated with light in the presence of a photosensitive radical polymerization initiator. Any of the compounds can be used, and typical examples include (meth) acrylate compounds, unsaturated polyester compounds, allylurethane compounds, polythiol compounds, and the like. Two or more kinds can be used. Among them, a compound having at least one (meth) acryl group in one molecule is preferably used. Specific examples include a reaction product of an epoxy compound and (meth) acrylic acid, and a (meth) acrylic alcohol. Examples include acid esters, urethane (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates.

  As a reaction product of the above-mentioned epoxy compound and (meth) acrylic acid, it can be obtained by reaction of an aromatic epoxy compound, an alicyclic epoxy compound and / or an aliphatic epoxy compound with (meth) acrylic acid (meta) ) Acrylate reaction products. Specific examples of the (meth) acrylate reaction product obtained by reacting an aromatic epoxy compound with (meth) acrylic acid include bisphenol compounds such as bisphenol A and bisphenol F or their alkylene oxide adducts and epoxy such as epichlorohydrin. (Meth) acrylate obtained by reacting glycidyl ether obtained by reaction with an agent with (meth) acrylic acid, (meth) acrylate-based reaction product obtained by reacting epoxy novolac resin with (meth) acrylic acid Things can be mentioned.

Examples of the (meth) acrylic acid esters of the alcohols described above include aromatic alcohols, aliphatic alcohols, alicyclic alcohols and / or their alkylene oxide adducts having at least one hydroxyl group in the molecule; Mention may be made of (meth) acrylates obtained by reaction with (meth) acrylic acid.
More specifically, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) a Relate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol poly (meth) acrylate [dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.], ethoxylation Examples thereof include pentaerythritol tetra (meth) acrylate and (meth) acrylates of alkylene oxide adducts of polyhydric alcohols such as diol, triol, tetraol and hexaol described above.
Among them, as the (meth) acrylate of alcohols, (meth) acrylate having two or more (meth) acryl groups in one molecule obtained by reaction of polyhydric alcohol and (meth) acrylic acid is preferably used. It is done.
Of the (meth) acrylate compounds described above, an acrylate compound is preferably used in view of the polymerization rate rather than a methacrylate compound.

  Examples of the urethane (meth) acrylate described above include (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester with an isocyanate compound. As the hydroxyl group-containing (meth) acrylic acid ester, a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction of an aliphatic dihydric alcohol and (meth) acrylic acid is preferable. As a specific example, 2-hydroxy Examples thereof include ethyl (meth) acrylate. Moreover, as said isocyanate compound, the polyisocyanate compound which has a 2 or more isocyanate group in 1 molecule like tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. is preferable.

Furthermore, examples of the polyester (meth) acrylate described above include polyester (meth) acrylate obtained by a reaction between a hydroxyl group-containing polyester and (meth) acrylic acid.
Moreover, as above-mentioned polyether (meth) acrylate, the polyether acrylate obtained by reaction of a hydroxyl-containing polyether and acrylic acid can be mentioned.

  Examples of the cationically polymerizable organic compound that can be used in the photocurable resin compositions of the above (b) and (c) include << 1 >> epoxy compounds such as alicyclic epoxy resins, aliphatic epoxy resins, and aromatic epoxy resins. << 2 >> Cyclic ether or cyclic acetal compound (oxetane compound, tetrahydrofuran, oxolane compound such as 2,3-dimethyltetrahydrofuran, trioxane, 1,3-dioxolane, 1,3,6-trioxane cyclooctane, etc.); << 3 >> cyclic lactone compounds (β-propiolactone, ε-caprolactone, etc.); << 4 >> thiirane compounds (ethylene sulfide, thioepichlorohydrin, etc.); << 5 >> thietane compounds (1,3-propyne sulfide, 3, 3-dimethylthietane); << 6 >> vinyl ether compound [ethylene Glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), triethylene glycol divinyl ether, etc.]; << 7 >> Reaction of epoxy compound with lactone Spiro orthoester compounds obtained by the following: << 8 >> Ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene and polybutadiene.

  Among these, as the cationically polymerizable organic compound, an epoxy compound [especially a polyepoxy compound (epoxy resin) having two or more epoxy groups in one molecule] is preferably used, and the epoxy compound and the oxetane compound are used in combination. Is more preferable. In particular, when an alicyclic polyepoxy compound (alicyclic epoxy resin) having two or more epoxy groups in one molecule is used in combination with an oxetane compound, the viscosity of the photo-curable resin composition is lowered and the molding is smoothly performed. In addition, the cationic polymerization rate, the thick film curability, the resolution, the ultraviolet transmittance, and the like are improved, and the volumetric shrinkage of the obtained optical three-dimensional model is reduced.

  Examples of the alicyclic epoxy resin (alicyclic polyepoxy compound) include polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring, or cyclohexene or cyclopentene ring-containing compound as hydrogen peroxide, peracid. Examples thereof include cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidation with a suitable oxidizing agent. More specifically, as the alicyclic epoxy resin (alicyclic polyepoxy compound), for example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane) The Black pentaerythritol diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexane carboxylate) and the like.

  Examples of the aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. And so on. More specifically, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl Ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, one or two aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ether of polyether polyol and diglycidyl ester of aliphatic long-chain dibasic acid obtained by adding the above alkylene oxide Etc. can be mentioned.

  Examples of the aromatic epoxy resin include mono- or polyglycidyl ethers of mono- or polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof. Glycidyl ether, epoxy novolac resin, phenol, cresol, butylphenol obtained by reaction of bisphenol A, bisphenol F or its alkylene oxide adduct with epichlorohydrin, or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these And so on.

As the oxetane compound described above, one or more of a monooxetane compound (OXm) having one oxetane group in the molecule and a polyoxetane compound (OXp) having two or more oxetane groups in the molecule are used. be able to.
As the monooxetane compound (OXm), any compound having one oxetane group in one molecule can be used. For example, trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3 -Methyl-3-phenoxymethyloxetane, monooxetane monoalcohol having one oxetane group and one alcoholic hydroxyl group in the molecule can be mentioned, among them, the reactivity, viscosity of the photocurable resin composition, etc. From this point, a monooxentane monoalcohol compound is preferably used.
In particular, among monooxetane monoalcohol compounds, a monooxetane compound (Ia) represented by the following general formula (Ia) and a monooxetane compound represented by the following general formula (Ib) ( At least one monooxetane compound selected from Ib) is preferably used from the viewpoints of availability, reactivity, and the like. In particular, when the monooxetane compound (Ib) represented by the following general formula (Ib) is used as the monooxetane compound (OXm), the water resistance of the resin composition for optical modeling and the three-dimensional modeled product obtained therefrom The property becomes better.

（式中、Ｒ¹およびＲ²は炭素数１〜５のアルキル基、Ｒ³はエーテル結合を有していてもよい炭素数２〜１０のアルキレン基、ｑは１〜６の整数を示す。）

(Wherein R ¹ and R ² are alkyl groups having 1 to 5 carbon atoms, R ³ is an alkylene group having 2 to 10 carbon atoms which may have an ether bond, and q is an integer of 1 to 6). )

In the above general formula (Ia), examples of R ¹ include methyl, ethyl, propyl, butyl, and pentyl. In the above general formula (Ia), q may be any one of 1 to 6, but 1 is preferable from the viewpoint of availability and reactivity.
Specific examples of the monooxetane compound (Ia) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl-3. -Normal butyl oxetane, 3-hydroxymethyl-3-propyl oxetane, etc. can be mentioned, These 1 type (s) or 2 or more types can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferably used from the viewpoints of easy availability and reactivity.

In the above general formula (Ib), examples of R ² include methyl, ethyl, propyl, butyl, and pentyl.
In the general formula (Ib), R ³ may be either a chain alkylene group or a branched alkylene group as long as it is an alkylene group having 2 to 10 carbon atoms, or an alkylene group ( It may be a C2-C10 chain or branched alkylene group having an ether bond (ether oxygen atom) in the middle of the (alkylene chain). Specific examples of R ³ include ethylene group, trimethylene group, tetramethylene group, ethoxyethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and 3-oxypentylene group. Among them, R ³ is preferably a trimethylene group, a tetramethylene group, a pentamethylene group, a heptamethylene group or an ethoxyethylene group from the viewpoints of ease of synthesis, ease of handling because the compound is liquid at room temperature.

As the polyoxetane compound (OXp), a compound having two or more oxetane groups, for example, a compound having two, three, or four oxetane groups can be used, and of these, two oxetane groups are included. Dioxetane compounds are preferably used.
In particular, as a dioxetane compound, the following general formula (b);

（式中、２個のＲ⁴は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁵は芳香環を有しているかまたは有していない２価の有機基、ｒは０または１を示す。）
で表されるジオキセタン化合物（II）が、入手の容易性、反応性、低吸湿性、得られる硬化物の力学的特性などの点から好ましく用いられる。

(In the formula, two R ⁴ are the same or different from each other, and the alkyl group having 1 to 5 carbon atoms, R ⁵ is a divalent organic group having or not having an aromatic ring, and r is 0 or 1) Is shown.)
The dioxetane compound (II) represented by the formula is preferably used from the viewpoints of availability, reactivity, low hygroscopicity, and mechanical properties of the resulting cured product.

In the above general formula (b), examples of R ⁴ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ⁵ include linear or branched alkylene groups having 1 to 12 carbon atoms (for example, ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc. ), A divalent group represented by the formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph—CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated A bisphenol Z residue, a cyclohexane dimethanol residue, a tricyclodecane dimethanol residue, etc. can be mentioned.

  Specific examples of the dioxetane compound (b) represented by the general formula (II) include dioxetane compounds represented by the following formula (II-a) or formula (II-b).

（式中、２個のＲ⁴は互いに同じか又は異なる炭素数１〜５のアルキル基、Ｒ⁵は芳香環を有しているかまたは有していない２価の有機基を示す。）

(In the formula, two R ^{4 's} are the same as or different from each other, and a C 1-5 alkyl group, and R ⁵ is a divalent organic group having or not having an aromatic ring.)

Specific examples of the dioxetane compound represented by the above formula (II-a) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, bis (3- Propyl-3-oxetanylmethyl) ether, bis (3-butyl-3-oxetanylmethyl) ether, and the like.
Further, specific examples of the dioxetane compound represented by the above formula (II-b) include, in the above formula (II-b), two R ^{4 s} are both methyl, ethyl, propyl, butyl or pentyl groups, R ⁵ is ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc.), formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph—CH ₂ - a divalent group represented, hydrogenated bisphenol a residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexane dimethanol residue, a dioxetane compound is tricyclodecane dimethanol residues Can be mentioned.
The resin composition for optical modeling can contain one or more of the dioxetane compounds described above.

Among them, as the polyoxetane compound (OXp), in the above formula (II-a), bis (3-methyl-3-oxetanylmethyl) ether in which two R ^{4 s} are both methyl groups or ethyl groups and / or Bis (3-ethyl-3-oxetanylmethyl) ether is preferably used from the viewpoints of availability, low hygroscopicity, mechanical properties of the cured product, etc., and in particular, bis (3-ethyl-3-oxetanylmethyl) ether Is more preferably used.

In the photocurable resin composition of the above (b) and (c), it has two or more epoxy groups in one molecule based on the mass of the cationically polymerizable organic compound contained in the photocurable resin composition. The polyepoxy compound (epoxy resin) is preferably contained in an amount of 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more.
Moreover, when the photocurable resin composition of said (b) and (c) contains an oxetane compound as a part of cationically polymerizable organic compound, content of an oxetane compound is the mass of a cationically polymerizable organic compound. Is preferably 1 to 70% by mass, and more preferably 1 to 60% by mass.
In the photocurable resin composition (c), the content ratio of radical polymerizable organic compound: cation polymerizable organic compound is preferably 9: 1 to 1: 9 in terms of mass ratio, and 8: More preferably, it is 2 to 2: 8.

  The photo-sensitive radical polymerization initiator (hereinafter referred to as “photo radical polymerization initiator”) contained in the photo-curable resin composition of (a) and (c) above is a radical-polymerizable organic compound when irradiated with light. Any polymerization initiator capable of initiating radical polymerization can be used, for example, phenyl ketone compounds such as 1-hydroxy-cyclohexyl phenyl ketone, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, 1-hydroxycyclohexyl phenyl ketone Benzyl or its dialkyl acetal compound, diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy-2- Methyl-propiophenone, p- Acetophenone compounds such as methylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, benzoin Benzoin such as isobutyl ether or its alkyl ether compounds, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, benzophenone compounds such as 4,4'-dichlorobenzophenone, thioxanthone, 2-methylthioxanthone 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropyl Examples include thioxanthone compounds such as thioxanthone.

  The photocurable resin compositions (a) and (c) preferably contain a radical photopolymerization initiator in a proportion of 0.5 to 10% by mass based on the mass of the photocurable resin composition. 1 to 5% by mass is more preferable.

The photo-sensitive cationic polymerization initiator (hereinafter referred to as “photo-cationic polymerization initiator”) contained in the photo-curable resin composition of (b) and (c) is a cationic polymerizable organic compound when irradiated with light. Any of the polymerization initiators that can initiate cationic polymerization can be used, such as triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide Bisdihexafluoroantimonate, bis- [4- (di4'-hydroxyethoxyphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdi Hexafluorophosphate, tetrafluoroboro Examples thereof include diphenyliodonium acid, and one or more of these can be used.
In addition, for the purpose of improving the reaction rate, a photosensitizer such as benzophenone, benzoin alkyl ether, thioxanthone or the like may be used together with the cationic polymerization initiator as necessary.

  The photocurable resin compositions (b) and (c) preferably contain a photocationic polymerization initiator in a proportion of 1 to 10% by mass based on the mass of the photocurable resin composition. It is more preferable to contain in the ratio of -6 mass%.

  The resin composition for optical modeling used for the production of an optical three-dimensional model is a colorant such as a pigment or a dye, an antifoaming agent, a leveling agent, a thickening agent, a flame retardant, an antioxidant, or a filler, if necessary. An appropriate amount of one or more kinds such as (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.) and a modifying resin can be contained.

The optical three-dimensional modeled object that is the object of the processing method of the present invention can be manufactured using a conventionally known optical three-dimensional modeled method and apparatus using a resin composition for optical modeling. As a representative example of the optical three-dimensional modeling method preferably employed in that case, a cured layer is obtained by selectively irradiating light so that a cured layer having a desired pattern is obtained on a liquid photocurable resin composition. Then, an uncured liquid photocurable resin composition is supplied to the cured layer, and a lamination operation in which a cured layer continuous with the cured layer is newly formed by irradiating active energy rays in the same manner. A method of finally obtaining a desired three-dimensional shaped object by repeating can be mentioned.
Examples of the light at that time include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies. Among them, ultraviolet rays having a wavelength of 300 to 400 nm are preferably used from an economical viewpoint. As a light source at that time, an ultraviolet laser (for example, a semiconductor-excited solid laser, an Ar laser, a He—Cd laser), a high-pressure mercury lamp is used. Ultra high pressure mercury lamps, low pressure mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light emitting diodes), ultraviolet fluorescent lamps, and the like can be used.

  In forming each cured resin layer having a predetermined shape pattern by irradiating light on the modeling surface made of the photocurable resin composition, point-drawing is performed using light focused in a spot shape such as laser light. Alternatively, a cured resin layer may be formed by a line drawing method, or light is applied to a modeling surface through a planar drawing mask formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter (DMD). You may employ | adopt the modeling system which irradiates planarly and forms a cured resin layer.

The optical three-dimensional object is generated by the processing method of the present invention that irradiates the optical three-dimensional object with light (α) including light having a wavelength in the range of 430 to 500 nm and not including light having a wavelength of 400 nm or less. In the case of an optical three-dimensional object with excellent transparency and colorlessness or a colorant that eliminates or reduces discoloration such as yellowing, an optical three-dimensional object that has the original excellent color tone can be easily and quickly The reason why it can be obtained smoothly is not clear, but is estimated as follows.
In other words, various substances that cause discoloration such as yellowing of an optical three-dimensional model can be considered, but radical polymerizable organic compounds, cationic polymerizable organic compounds, photosensitive radical polymerization initiators, photosensitive cationic polymerization initiation In the compound used as an agent, there is a compound that changes to a substance colored yellow or the like when irradiated with ultraviolet rays, etc., and the substance absorbs in the blue region by ultraviolet irradiation during optical three-dimensional modeling. It changes to a substance that causes discoloration, and discoloration such as yellowing occurs in the optical three-dimensional object obtained by optical three-dimensional modeling, and the optical three-dimensional object that causes such discoloration such as yellowing On the other hand, when light (α) containing light (blue light) having a wavelength in the range of 430 to 500 nm and not containing light having a wavelength of 400 nm or less is irradiated, discoloration such as yellowing The causative substance absorbs blue light, undergoes reactions such as photolysis and photoisomerization, changes to a colorless substance, and discoloration such as yellowing that occurred in optical three-dimensional objects is eliminated or reduced, It is presumed that an optical three-dimensional object having excellent colorlessness and an optical three-dimensional object having a color tone inherent to the colorant is presumed.
At that time, one of the causes of discoloration such as yellowing is a conjugated double bond structure produced by irradiating a compound having a benzoyl group, an aromatic compound, a compound having an acryloyl group or the like with ultraviolet rays, or a polymer network. An isolated radical species confined in the region can be considered.

  The optical three-dimensional object obtained by processing with the method of the present invention can be widely used in various fields, and is not limited at all. Shape verification model for verifying the function, functional test model for checking the functionality of parts, master model for producing molds, master model for producing molds, direct mold for prototype molds, art It can be used as a craft. More specifically, for example, precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, etc. models, master molds, models for processing, complex heat transfer circuit designs Effectively used for applications such as parts for construction, parts for analysis and planning of heat transfer behavior of complex structures, restoration of artworks, imitation and contemporary art, art and crafts such as design presentation models for glass-walled buildings Can do.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
In the following examples, measurement of viscosity, depth of cure (Dp), critical curing energy (Ec) and work curing energy (E ₁₀ ) of photocurable resin composition, and optical three-dimensional modeled object obtained by optical modeling Mechanical properties [tensile properties (tensile rupture strength, tensile rupture elongation, tensile modulus), yield strength, bending properties (bending strength, flexural modulus), impact strength], shrinkage rate, hardness, thermal deformation temperature, optical Total light irradiation intensity Q of light in the wavelength range (visible light range) of 380 to 780 nm on the surface irradiated with light in the three-dimensional modeled object (hereinafter sometimes referred to as “total irradiation intensity Q of visible light”), exposure The wavelength range of light emitted from the apparatus, the total irradiation intensity of light having a wavelength of 430 to 500 nm on the surface irradiated with light in the optical three-dimensional object (hereinafter referred to as “total irradiation intensity of light (430 to 500 nm)”) Sometimes ) And the yellowness of the optical three-dimensional object were measured or calculated as follows.

(1) Viscosity of photocurable resin composition:
After putting a photocurable resin composition in a 25 degreeC thermostat and adjusting the temperature of a photocurable resin composition to 25 degreeC, it uses a B-type viscometer (made by Toki Sangyo Co., Ltd.) and rotational speed. Measured at 20 rpm.

(2) Curing depth (Dp), critical curing energy (Ec) and work curing energy (E ₁₀ ) of the photocurable resin composition:
Measurement was performed according to the theory described in Non-Patent Document 1. Specifically, a laser beam (ultraviolet light with a wavelength of 355 nm, a liquid surface laser intensity of 100 mW) of a semiconductor-excited solid laser is applied to a modeling surface (liquid surface) made of a photocurable resin composition, and the irradiation speed is changed in six steps ( The photocured film was formed by irradiating with the irradiation energy amount changed by 6 levels. The produced photocured film was taken out from the photocurable resin composition liquid, the uncured resin was removed, and the thickness of the cured film corresponding to 6 levels of energy was measured with a vernier caliper. Plotting the photocured film thickness as the Y-axis and the irradiation energy amount as the X-axis (logarithmic axis), obtaining the cure depth [Dp (mm)] from the slope of the straight line obtained by plotting, and intercepting the X-axis Was the critical curing energy [Ec (mJ / cm ² )], and the exposure energy required to cure to a thickness of 0.25 mm was the work curing energy [(E ₁₀ / (mJ / cm ² )].

(3) Tensile properties (tensile rupture strength, tensile rupture elongation, tensile elastic modulus) of the optical three-dimensional structure:
An optical three-dimensional object (dumbbell-shaped test piece based on JIS K-7113) [ultraviolet ray (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) irradiated in 20 minutes for 20 minutes. The test piece was measured for tensile strength at break (tensile strength), tensile elongation at break (tensile elongation), and tensile modulus according to JIS K-7113.

(4) Yield strength of optical 3D objects:
In the tensile property test of (3) above, the yield strength is defined as the strength at which the optical three-dimensional structure moves from elasticity to plasticity.

(5) Bending characteristics (bending strength, bending elastic modulus) of the optical three-dimensional structure:
An optical three-dimensional model (bar-shaped test piece conforming to JIS K-7171) [ultraviolet ray (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) irradiated in 20 minutes for 20 minutes. Was used to measure the bending strength and the flexural modulus of the test piece according to JIS K-7171.

(6) Impact strength of the optical three-dimensional object:
Optical three-dimensional modeled object (rectangular test piece conforming to JIS K-7110) [UV light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) irradiated for 20 minutes Was used to measure the notched Izod impact strength of the test piece according to JIS K-7110.

(7) Shrinkage rate:
The specific gravity (d ₀ ) of the photo-curable resin composition (liquid) before photo-curing, and the photo-cured product obtained by photo-curing the ultraviolet ray (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) 20 From the specific gravity (d ₁ ) of what was post-cured by irradiation for minutes, the shrinkage rate was determined by the following formula.

Shrinkage rate (%) = {(d ₁ −d ₀ ) / d ₁ } × 100

(8) Hardness of optical three-dimensional structure (Shore D hardness):
Optically three-dimensional modeled objects (dumbbell-shaped test pieces conforming to JIS K-7113) [ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) irradiated for 20 minutes were prepared in the following examples and comparative examples. The post-cured] hardness (Shore D hardness) is measured by a durometer method at 25 ° C. using an “Asker D-type hardness meter” manufactured by Kobunshi Keiki Co., Ltd. according to JIS K-6253. did.

(9) Thermal deformation temperature of the optical three-dimensional structure:
An optical three-dimensional model (bar-shaped test piece conforming to JIS K-7171) [ultraviolet ray (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) irradiated in 20 minutes for 20 minutes. In accordance with JIS K-7207 (Method A), a load of 1.81 MPa is applied to the test piece using “HDT Tester 6M-2” manufactured by Toyo Seiki Co., Ltd. The heat distortion temperature of was measured.

(10) Total irradiation intensity Q of visible light:
Optical three-dimensional modeled object (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm rectangular parallelepiped) [what was post-cured by irradiation with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) for 20 minutes] On a flat table, two rectangular surfaces of length x width = 50 mm x 30 mm are placed so that the upper surface and the lower surface are the upper and lower surfaces. A probe of an irradiance meter (“HD2302” manufactured by Tsuruga Electric Co., Ltd.) is attached to a position substantially corresponding to the intersection of the optical three-dimensional object, and light is irradiated onto the optical three-dimensional object from above the optical three-dimensional object. The total irradiation intensity Q (W / m ² ) in the wavelength range (visible light region) of 380 to 780 nm on the surface irradiated with the light of the shaped article was measured.

(11) Total irradiation intensity of light (430 to 500 nm):
(11-i) At the time of light irradiation to the optical three-dimensional modeled object in (10) above, the probe of the optical spectrum analyzer ("AQ-6611" manufactured by Ando Electric Co., Ltd.) is used. X30 mm square upper surface is mounted side by side with the probe of the irradiance meter ("HD2302" manufactured by Tsuruga Electric Co., Ltd.) at a position substantially corresponding to the intersection of the diagonal lines on the surface irradiated with the light of the optical three-dimensional object. The relative spectral intensity curve F was determined by measuring the relative spectral intensity in 5 nm increments over a wavelength range of 340 to 850 nm (visible light range).
(11-ii) from the relative spectral intensity curve F obtained in the above (11-i), the integral value L _A and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380 to 780 nm (visible light region) calculating the relative spectral intensity integrated value L _B, respectively, wherein: a _{Q × (L B / L a} ), the sum of the light having a wavelength 430~500nm at the surface being irradiated with light of an optical three-dimensional object Irradiation intensity (W / m ² ) was determined.

(12) Wavelength range and peak intensity of light emitted from the light source:
From the relative spectral intensity curve F obtained in (11-i) above, the wavelength range and peak intensity of light emitted from the light source were obtained.

(13) Measurement of yellowness:
Optical three-dimensional modeled object (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm rectangular parallelepiped) obtained by performing optical three-dimensional modeling in the following examples and comparative examples [UV (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) for 20 minutes after irradiation, the yellowness before the post-treatment by light irradiation and the yellowness after the post-treatment by light irradiation over a predetermined time are 60 mm in diameter. It is attached to a spectrophotometer ("H-3900H" manufactured by Hitachi High-Technologies Corporation) equipped with an integrating sphere, and the spectral transmittance with a plate thickness of 5 mm is measured, and the spectral transmittance thus obtained is applied to the spectrophotometer. By using the attached software (UV Solutions) to perform numerical calculations according to the method defined in JIS-K7373, in the condition of auxiliary illuminant C, field of view of 2 degrees. To determine the chromaticity.

Example 1
(1) Preparation of photocurable resin composition:
(I) 60 parts by mass of hydrogenated bisphenol A diglycidyl ether (“HBE-100” manufactured by Shin Nippon Chemical Co., Ltd.), 5 mass of 3-hydroxymethyl-3-ethyloxetane (“OXT-101” manufactured by Toagosei Co., Ltd.) Parts, bis (3-ethyl-3-oxetanylmethyl) ether (“OXT-221” manufactured by Toagosei Co., Ltd.), 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate (“CPI-101A manufactured by San Apro Co., Ltd.) ]) (Cationic polymerization initiator) 4 parts by mass, dipentaerythritol polyacrylate (Shin Nakamura Chemical Co., Ltd. "A-9550") 10 parts by mass, lauryl acrylate (Shin Nakamura Chemical Co., Ltd.) 6 parts by mass, 1-Hydroxy-cyclohexyl phenyl ketone (Ciba Specialty) A photo-curable resin composition was prepared by thoroughly mixing 3 parts by mass of “Irgacure 184” (radical polymerization initiator) manufactured by Chemical Co., and accommodated in a light-shielded tank.
(Ii) The viscosity of the photocurable resin composition obtained in the above (i) was measured by the method described above, and was 200 mPa · s.
(Iii) About the photocurable resin composition obtained in the above (i), the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) were determined by the above-described method. Depth (Dp) = 0.2 mm, critical curing energy (Ec) = 22 mJ / cm ² , and work curing energy (E ₁₀ ) = 79 mJ / cm ² .

(2) Manufacture of an optical three-dimensional model for measuring physical properties:
(I) Using the photocurable resin composition prepared in (i) of (1) above, “Semiconductor excitation” manufactured by SpectraPhysics Co., Ltd. using an ultra-high-speed stereolithography system (“SOLIFORM 500B” manufactured by Nabtesco Corporation) solid laser BL6 type "; irradiated perpendicularly (output 1000mW wavelength 355 nm) of the surface, under the conditions of irradiation energy 100 mJ / cm ^2, slice pitch (lamination thickness) 0.10 mm, the average modeling per layer Performs optical three-dimensional modeling in 2 minutes and mechanical properties [tensile properties (tensile rupture strength, tensile rupture elongation, tensile elastic modulus), yield strength, bending properties (bending strength, bending elastic modulus), impact strength], An optical three-dimensional object for measuring shrinkage rate, hardness (Shore D hardness) and thermal deformation temperature is manufactured, and ultraviolet light is applied to the obtained optical three-dimensional object (test piece). And post cured by irradiation with intensity 30 W / m ²⁾ 20 minutes; high pressure mercury lamp) (wavelength 365 nm.
(Ii) Various physical properties were measured by the above-described method using the optical three-dimensional structure obtained in (i) above (post-cured with ultraviolet rays). Tensile breaking strength = 49 MPa, tensile breaking elongation = 6.8%, tensile elastic modulus = 1690 MPa, yield strength = 43 MPa, bending strength = 65 MPa, bending elastic modulus = 2010 MPa, impact strength = 1.6 kJ / m ² , shrinkage rate = 5.4%, hardness (Shore D hardness) ) = 84 and heat distortion temperature = 50 ° C.

(3) Light irradiation treatment of optical three-dimensional structure:
(I) Using the photocurable resin composition prepared in (i) of (1) above, adopting the same optical modeling conditions as in (i) of (2) above, an optical three-dimensional model (vertical x horizontal) × Thickness = 50 mm × 30 mm × 5 mm rectangular parallelepiped) was manufactured, and then this optical three-dimensional model was post-cured by irradiating with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) for 20 minutes.
The resulting optically three-dimensional molded article after post-curing with ultraviolet rays was transparent as a whole, but yellowed, and the yellowness measured by the above-described method was 2.9.
(Ii) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional object obtained in (i) above (post-cured by ultraviolet irradiation). Light source (light-emitting diode) that emits blue light, placed on the top and bottom surfaces (LED Paradise “LP-R5B40”, wavelength range of emitted light = 420 to 505 nm, peak wavelength = 455 nm, wavelength 400 nm 100 pieces of the following (without emitting the following light) were collected in a square shape and each was supplied with 15 mA, and blue light was irradiated from above the optical three-dimensional object for 5 hours.
(Iii) Upon irradiation with the blue light of (ii) above, the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light region) on the surface of the optical three-dimensional object is described above. while measured by a method, the integral value L _a and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380~780nm at the surface being irradiated with light of an optical three-dimensional object (visible light region) seeking relative spectral intensity of the integrated value L _B in the manner described above, wherein: the _{Q × (L B / L a} ), a wavelength 430~500nm at the surface being irradiated with light of an optical three-dimensional object When the total irradiation intensity (W / m ² ) of light was determined, it was as shown in Table 1 below.
(Iv) In addition, when the blue light is irradiated in (ii) above, the yellowness of the optical three-dimensional object is obtained after irradiation with blue light for 30 minutes, irradiation for 2 hours, and irradiation for 5 hours. Was measured by the method described above, and was as shown in Table 1 below.

Example 2
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. To produce an optical three-dimensional model (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm cuboid), and then apply ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) to this optical three-dimensional model. Post-cured by irradiation for 20 minutes.
The optically three-dimensional molded article after post-curing with ultraviolet rays obtained in this way was transparent as a whole, but yellowed, and the yellowness measured by the method described above was 2.7.
(2) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional structure obtained in (1) (postcured by ultraviolet irradiation). Light source (light emitting diode) that emits blue-green light placed on the upper and lower surfaces (LED Paradise “AQ-L5030BGC”, wavelength range of emitted light = 455-565 nm, peak wavelength = 505 nm, wavelength 400 nm 100 pieces (without emitting the following light) were collected in a square shape and each was energized with 15 mA, and blue-green light was irradiated for 5 hours from above the optical three-dimensional object.
(3) Upon irradiation with blue-green light in (2) above, the total irradiation intensity Q (W / m ² ) in the wavelength range (visible light range) of 380 to 780 nm on the surface of the optical three-dimensional object is described above. while measured by a method, the integral value L _a and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380~780nm at the surface being irradiated with light of an optical three-dimensional object (visible light region) seeking relative spectral intensity of the integrated value L _B in the method described above, wherein: the _{Q × (L B / L a} ), a wavelength 430~500nm at the surface being irradiated with light of a stereolithography product The total irradiation intensity (W / m ² ) of light was determined and as shown in Table 1 below.
(4) In addition, when the blue-green light is irradiated in (2) above, the yellowness of the optical three-dimensional object is obtained after irradiating with blue-green light for 30 minutes, after irradiation for 2 hours, and after irradiation for 5 hours. Was measured by the method described above, and was as shown in Table 1 below.

Example 3
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. To produce an optical three-dimensional model (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm cuboid), and then apply ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) to this optical three-dimensional model. Post-cured by irradiation for 20 minutes.
The optically three-dimensional molded article after post-curing with ultraviolet rays obtained in this way was transparent as a whole, but yellowed, and the yellowness measured by the method described above was 2.7.
(2) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional structure obtained in (1) (postcured by ultraviolet irradiation). A light source (light emitting diode) that is placed so as to be on the upper and lower surfaces and emits white light (“LP-508H196WC-1” manufactured by LED Paradise, wavelength range of radiated light = 415 to 740 nm, peak wavelength = 450 nm and 100 pieces of 540 nm (without emitting light having a wavelength of 400 nm or less) were collected in a rectangular shape and each was supplied with 15 mA, and white light was irradiated from above the optical three-dimensional object for 5 hours.
(3) Upon irradiation with white light in (2) above, the total irradiation intensity Q (W / m ² ) in the wavelength range (visible light range) of 380 to 780 nm on the surface of the optical three-dimensional object is described above. while measured by a method, the integral value L _a and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380~780nm at the surface being irradiated with light of an optical three-dimensional object (visible light region) seeking relative spectral intensity of the integrated value L _B in the manner described above, wherein: the _{Q × (L B / L a} ), a wavelength 430~500nm at the surface being irradiated with light of an optical three-dimensional object When the total irradiation intensity (W / m ² ) of light was determined, it was as shown in Table 1 below.
(4) In addition, when irradiating the blue-green light of (2) above, the yellowness of the optical three-dimensional object is obtained after irradiation with white light for 30 minutes, irradiation for 2 hours, and irradiation for 5 hours. Was measured by the method described above, and was as shown in Table 1 below.

Example 4
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. To produce an optical three-dimensional model (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm cuboid), and then apply ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) to this optical three-dimensional model. Post-cured by irradiation for 20 minutes.
The optically three-dimensional molded article after post-curing with ultraviolet rays obtained in this manner was transparent as a whole, but yellowed, and the yellowness measured by the method described above was 3.0.
(2) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional structure obtained in (1) (postcured by ultraviolet irradiation). The metal halide lamp ("USHIOLIGHTING" GL-30201BF "as a light source, wavelength range of emitted light: lower limit 360nm and upper limit 780nm exceeded, peak wavelength = 365nm, 405nm, 420nm, 435 nm, 545 nm, 580 nm, 640 nm), and an ultraviolet cut plate made of acrylic (“Acrylite N549” manufactured by Mitsubishi Rayon Co., Ltd.) below the light source, the removal rate of light having a wavelength of 400 nm or less contained in the light emitted from the light source = 99.92%), and the light after the ultraviolet rays were cut from above the optical three-dimensional object was spread over 5 hours. It was irradiated Te.
(3) The above-described method of the total irradiation intensity Q (W / m ² ) in the wavelength range (visible light range) of 380 to 780 nm on the surface of the optical three-dimensional structure at the time of the light irradiation of ( ² ) above. And the integral value L _A of the relative spectral intensity in the wavelength range (visible light range) of 380 to 780 nm on the surface irradiated with the light of the optical three-dimensional object and the wavelength range of 430 to 500 nm. The integral value L _B of the relative spectral intensity is obtained by the method described above, and the light having a wavelength of 430 to 500 nm on the surface irradiated with the light of the optical three-dimensional structure is obtained from the formula: Q × (L _B / L _A ) The total irradiation intensity (W / m ² ) was determined as shown in Table 1 below.
(4) In addition, when irradiating with the light of (2) above, after irradiating with light for 30 minutes, after irradiating for 2 hours and after irradiating for 5 hours, the yellowness of the optical three-dimensional object is determined as described above. It was as shown in following Table 1 when it measured by the method which carried out.

<< Comparative Example 1 >>
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. To produce an optical three-dimensional model (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm cuboid), and then apply ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) to this optical three-dimensional model. Post-cured by irradiation for 20 minutes.
The resulting optically three-dimensional molded article after post-curing with ultraviolet rays was transparent as a whole, but yellowed, and the yellowness measured by the above-described method was 2.9.
(2) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional structure obtained in (1) (postcured by ultraviolet irradiation). Light source that emits red light (light emitting diode) placed on the top and bottom surfaces (“TLRE180AP” manufactured by Toshiba Corporation, wavelength range of radiation light = 600 to 675 nm, peak wavelength = 645 nm, wavelength 400 nm or less 100 pieces of light (without emitting light) were collected in a square and each was energized with 15 mA, and red light was irradiated for 5 hours from above the optical three-dimensional object.
(3) Upon irradiation with red light in (2) above, the total irradiation intensity Q (W / m ² ) in the wavelength range (visible light region) of 380 to 780 nm on the surface of the optical three-dimensional object is described above. while measured by a method, the integral value L _a and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380~780nm at the surface being irradiated with light of an optical three-dimensional object (visible light region) seeking relative spectral intensity of the integrated value L _B in the manner described above, wherein: the _{Q × (L B / L a} ), a wavelength 430~500nm at the surface being irradiated with light of an optical three-dimensional object When the total irradiation intensity (W / m ² ) of light was determined, it was as shown in Table 2 below.
(4) In addition, when the red light is irradiated in (2) above, the yellowness of the optical three-dimensional object is obtained after irradiation with red light for 30 minutes, irradiation for 2 hours, and irradiation for 5 hours. Was measured by the method described above and was as shown in Table 2 below.

<< Comparative Example 2 >>
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. To produce an optical three-dimensional model (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm cuboid), and then apply ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) to this optical three-dimensional model. Post-cured by irradiation for 20 minutes.
The resulting optically three-dimensional molded article after post-curing with ultraviolet rays was transparent as a whole, but yellowed, and the yellowness measured by the above-described method was 2.9.
(2) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional structure obtained in (1) (postcured by ultraviolet irradiation). Light source (light-emitting diode) that emits yellow-green light, placed on the top and bottom surfaces (Toshiba Corporation “TLGE183P”, wavelength range of emitted light = 530-595 nm, peak wavelength = 570 nm, wavelength 400 nm or less 100 pieces of light (without emitting light) were collected in a rectangular shape and each of them was energized with 15 mA, and yellow-green light was irradiated over 5 hours from above the optical three-dimensional object.
(3) The above-mentioned total irradiation intensity Q (W / m ² ) in the wavelength range (visible light range) of 380 to 780 nm on the surface of the optical three-dimensional structure is described above when the yellow-green light is irradiated in ( ² ) above. while measured by a method, the integral value L _a and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380~780nm at the surface being irradiated with light of an optical three-dimensional object (visible light region) seeking relative spectral intensity of the integrated value L _B in the manner described above, wherein: the _{Q × (L B / L a} ), a wavelength 430~500nm at the surface being irradiated with light of an optical three-dimensional object When the total irradiation intensity (W / m ² ) of light was determined, it was as shown in Table 2 below.
(4) In addition, when yellow-green light is irradiated in (2) above, yellowness of the optical three-dimensional object is obtained at the time after irradiation with yellow-green light for 30 minutes, after irradiation for 2 hours, and after irradiation for 5 hours. Was measured by the method described above and was as shown in Table 2 below.

<< Comparative Example 3 >>
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. To produce an optical three-dimensional model (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm cuboid), and then apply ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) to this optical three-dimensional model. Post-cured by irradiation for 20 minutes.
The optically three-dimensional molded article after post-curing with ultraviolet rays obtained in this way was transparent as a whole, but yellowed, and the yellowness measured by the method described above was 2.7.
(2) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional structure obtained in (1) (postcured by ultraviolet irradiation). Light source (light emitting diode) that emits green light, placed on the upper and lower surfaces (Toyoda Gosei Co., Ltd. “E1L53-AG0A2-04”, wavelength range of emitted light = 465 to 610 nm, peak wavelength = 525 nm 100 pieces of light having a wavelength of 400 nm or less were collected in a rectangular shape and each of which was energized with 15 mA was irradiated with green light from above the optical three-dimensional object for 5 hours.
(3) Upon irradiation with green light in (2) above, the total irradiation intensity Q (W / m ² ) in the wavelength range (visible light region) of 380 to 780 nm on the surface of the optical three-dimensional object is described above. while measured by a method, the integral value L _a and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380~780nm at the surface being irradiated with light of an optical three-dimensional object (visible light region) seeking relative spectral intensity of the integrated value L _B in the manner described above, wherein: the _{Q × (L B / L a} ), a wavelength 430~500nm at the surface being irradiated with light of an optical three-dimensional object When the total irradiation intensity (W / m ² ) of light was determined, it was as shown in Table 2 below.
(4) In addition, when the green light is irradiated in (2) above, the yellowness of the optical three-dimensional object is obtained after irradiation with red light for 30 minutes, irradiation for 2 hours, and irradiation for 5 hours. Was measured by the method described above and was as shown in Table 2 below.

<< Comparative Example 4 >>
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. To produce an optical three-dimensional model (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm cuboid), and then apply ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) to this optical three-dimensional model. Post-cured by irradiation for 20 minutes.
The resulting optically three-dimensional molded article after post-curing with ultraviolet rays was transparent as a whole, but yellowed, and the yellowness measured by the above-described method was 2.9.
(2) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional structure obtained in (1) (postcured by ultraviolet irradiation). A light source (light emitting diode) that emits near-ultraviolet light, placed on the upper and lower surfaces (LED Paradise “LP-R5UV400”, wavelength range of emitted light = 380 to 435 nm, peak wavelength = 400 nm) 100 pieces were collected in a rectangular shape and each was energized with 15 mA, and irradiated with near ultraviolet light from above the optical three-dimensional object for 5 hours.
(3) Upon irradiation with near-ultraviolet light in (2) above, the total irradiation intensity Q (W / m ² ) in the wavelength range (visible light range) of 380 to 780 nm on the surface of the optical three-dimensional structure is described above. while measured by the method, the integrated value L _a and the wavelength range of 430~500nm the relative spectral intensity in the wavelength range of 380~780nm at the surface being irradiated with light of a stereolithography object (visible light region) seeking a way that the integral value L _B of the relative spectral intensity above in the formula: wavelength from _{Q × (L B / L a} ), the surface being irradiated with light of an optical three-dimensional object 430~500nm The total irradiation intensity (W / m ² ) of light was determined as shown in Table 2 below.
(4) Further, at the time of irradiation of near ultraviolet light in the above (2), after irradiation with near ultraviolet light for 30 minutes, irradiation for 2 hours, and after irradiation for 5 hours, When the yellowness was measured by the method described above, it was as shown in Table 2 below.

<< Comparative Example 5 >>
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. To produce an optical three-dimensional model (vertical x horizontal x thickness = 50 mm x 30 mm x 5 mm cuboid), and then apply ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) to this optical three-dimensional model. Post-cured by irradiation for 20 minutes.
The resulting optically three-dimensional molded article after post-curing with ultraviolet rays was transparent as a whole, but yellowed, and the yellowness measured by the above-described method was 2.9.
(2) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional structure obtained in (1) (postcured by ultraviolet irradiation). The metal halide lamp ("GL-30201BF" manufactured by Ushi Lighting Co., Ltd., wavelength range of emitted light = 360 to 780 nm, peak wavelengths = 365 nm, 405 nm, 420 nm, 435 nm, 545 nm) 580 nm and 640 nm), and light from a light source (light including ultraviolet rays) was irradiated as it was for 2 hours from above the optical three-dimensional object.
(3) The above-described method of the total irradiation intensity Q (W / m ² ) in the wavelength range (visible light range) of 380 to 780 nm on the surface of the optical three-dimensional structure at the time of the light irradiation of ( ² ) above. And the integral value L _A of the relative spectral intensity in the wavelength range (visible light range) of 380 to 780 nm on the surface irradiated with the light of the optical three-dimensional object and the wavelength range of 430 to 500 nm. The integral value L _B of the relative spectral intensity is obtained by the method described above, and the light having a wavelength of 430 to 500 nm on the surface irradiated with the light of the optical three-dimensional structure is obtained from the formula: Q × (L _B / L _A ) The total irradiation intensity (W / m ² ) was determined as shown in Table 2 below.
(4) In addition, when the light of the above (2) was irradiated with light for 30 minutes and after the irradiation for 2 hours, the yellowness of the optical three-dimensional model was measured by the method described above. As shown in Table 2 below.

As seen in Table 1 above, in Examples 1 to 4, with respect to the optically three-dimensional object with yellowing produced by using the photocurable resin composition, it is within the range of 430 to 500 nm. Light that includes light having a wavelength and that does not include light having a wavelength of 400 nm or less was 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 was 15 W / m ² or more. As a result, after the irradiation for 5 hours, the yellowness of the optical three-dimensional model was all 2.4 or less, and the yellowness decreased by 18.5% or more of the initial yellowness. When the optical three-dimensional modeled objects of Examples 1 to 4 after irradiation for 5 hours were observed with the naked eye, the yellowing rate was extremely low and it was almost colorless and transparent.

On the other hand, as shown in Table 2, in Comparative Examples 1 to 3, the optical three-dimensional object was irradiated with light having a wavelength of 400 nm or less (particularly ultraviolet rays), but the total of light having a wavelength of 430 to 500 nm. Since the irradiation intensity was less than 15 W / m ² , the yellowness after irradiation for 5 hours has decreased by about 3 to 10% of the original, and the effect of improving yellowing is extremely small.
Further, in Comparative Examples 4 and 5, the yellowness of the optical three-dimensional modeled object is obtained regardless of the total irradiation intensity of light having a wavelength of 430 to 500 nm due to irradiation including light having a wavelength of 400 nm or less (particularly ultraviolet rays). Is significantly higher than before irradiation, and the degree of yellowing is rather greatly increased.

Example 5
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. A plurality of optical three-dimensional objects (vertical × horizontal × thickness = 50 mm × 30 mm × 5 mm rectangular parallelepiped) are manufactured, and ultraviolet light (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) is then applied to these optical three-dimensional objects. ) For 20 minutes to post cure.
The resulting optically three-dimensional molded article after post-curing with ultraviolet rays was transparent as a whole, but yellowed, and the yellowness measured by the above method was 2.9.
(2) The same blue light as used in (3) of Example 1 is radiated to each optical three-dimensional object obtained by (1) above (post-cured by ultraviolet irradiation). Blue light is emitted using 100 light sources (LED Paradise “LP-R5B40”) integrated in a rectangular shape and energized with 15 mA each, and at that time, a pulse width modulation device (PWM device) (AQ-224W-K, manufactured by Audio-Q, 2A pulse LED dimming kit for 24V) and constant voltage power supply, dimming of blue light (irradiation intensity The total irradiation intensity of light having a wavelength of 430 to 500 nm on the surface of the optical three-dimensional object is changed to 40.8 W / m ² , 15.1 W / m ² and 2.8 w / m ^2. Irradiation experiment was carried out and light was irradiated for 30 minutes. Once after irradiation after and 5 hours were, the yellowness of the stereolithography was measured in the manner described above.
The results are shown in Table 3 below together with the results of Example 1 described above.

Example 6
(1) Preparation of photocurable resin composition:
(I) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (“UVR-6105” manufactured by Dow Chemical Co.), ethoxylated bisphenol A diglycidyl ether (“BPO manufactured by Shin Nippon Rika Co., Ltd.) -20E ") 20 parts by mass, 10 parts by mass of 3-hydroxymethyl-3-ethyloxetane (" OXT-101 "manufactured by Toagosei Co., Ltd.), 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate (San Apro Corporation" CPI-101A ") (cationic polymerization initiator) 4 parts by mass, tricyclodecane dimethanol diacrylate (Shin Nakamura Chemical Co., Ltd." A-DCP ") 10 parts by mass, ethoxylated bisphenol A diacrylate (Shin Nakamura Chemical) "A-BPE-4" manufactured by Kogyo Co., Ltd. 10 parts by mass, 10 parts by mass of propoxylated pentaerythritol tetraacrylate (“ATM-4P” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1-hydroxy-cyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) (start of radical polymerization) Agent) A photocurable resin composition was prepared by thoroughly mixing 1.5 parts by mass, and this was stored in a light-shielded tank.
It was 340 mPa * s when the viscosity of the photocurable resin composition obtained by this was measured by the above-mentioned method.
(Ii) About the photocurable resin composition obtained in the above (i), the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) were determined by the above-described method. Depth (Dp) = 0.23 mm, critical curing energy (Ec) = 21 mJ / cm ² , and work curing energy (E ₁₀ ) = 65 mJ / cm ² .

(2) Manufacture of an optical three-dimensional model for measuring physical properties:
(I) Using the photocurable resin composition prepared in (i) of (1) above, optical three-dimensional modeling is performed in the same manner as (i) of (2) of Example 1 to obtain mechanical properties [ Tensile properties (tensile breaking strength, tensile elongation at break, tensile modulus), yield strength, bending properties (bending strength, bending modulus), impact strength], shrinkage, hardness (Shore D hardness) and heat distortion temperature Each of the optical three-dimensional objects to be manufactured was manufactured, and the obtained optical three-dimensional object (test piece) was irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) for 20 minutes to be post-cured. .
(Ii) Various physical properties were measured by the above-described method using the optical three-dimensional structure obtained in (i) above (post-cured with ultraviolet rays). Tensile breaking strength = 61 MPa, tensile breaking elongation = 5.1%, tensile elastic modulus = 2050 MPa, yield strength = 54 MPa, bending strength = 84 MPa, bending elastic modulus = 2820 MPa, impact strength = 1.5 kJ / m ² , shrinkage rate = 5.4%, hardness (Shore D hardness) ) = 87 and heat distortion temperature = 47 ° C.

(3) Light irradiation treatment of optical three-dimensional structure:
(I) Using the photocurable resin composition prepared in (i) of (1) above, adopting the same optical modeling conditions as (i) of (2) of Example 1 to create an optical three-dimensional model ( (Vertical x Horizontal x Thickness = 50mm x 30mm x 5mm rectangular parallelepiped) and then UV curing (High pressure mercury lamp) (wavelength 365nm; intensity 30W / m ² ) for 20 minutes did.
The optically three-dimensional molded article after post-curing with ultraviolet rays obtained by this was almost transparent, but yellowed, and the yellowness measured by the method described above was 6.0.
(Ii) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional object obtained in (i) above (post-cured by ultraviolet irradiation). The same light source as used in Example 1, which is placed on the upper and lower surfaces and emits blue light (“LP-R5B40” manufactured by LED Paradise, wavelength range of emitted light = 420 to 505 nm, peak wavelength = 455 nm, which does not emit light with a wavelength of 400 nm or less), and each of which is energized with 15 mA, is irradiated with blue-green light from above the optical three-dimensional object for 2 hours. When the yellowness of the optical three-dimensional model was measured by the method described above at the time after irradiation for 2 hours, it was as shown in Table 4 below.
At that time, the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light region), the wavelength range of 380 to 780 nm (visible) on the surface irradiated with the light of the optical three-dimensional object. The integrated value L _A of the relative spectral intensity in the light region) and the integrated value L _B of the relative spectral intensity in the wavelength range of 430 to 500 nm were the same as in Example 1.

Example 7
(1) Preparation of photocurable resin composition:
(I) Hydrogenated bisphenol A diglycidyl ether (30.75 parts by mass of “HBE-100” manufactured by Shin Nippon Chemical Co., Ltd.), 22 masses of ethoxylated bisphenol A diglycidyl ether (“BPO-20E” manufactured by Nippon Steel Chemical Co., Ltd.) Parts, 4-phenylthiophenyl diphenylsulfonium hexafluoroantimonate (“CPI-101A” manufactured by San Apro Co., Ltd.) (cation polymerization initiator), dipentaerythritol polyacrylate (“N-Nakamura Chemical Co., Ltd.“ A- 9550 ") 8 parts by mass, dipentaerythritol hexaacrylate (" Kayarad DPHA "manufactured by Nippon Kayaku Co., Ltd.) 4 parts by mass, 1-hydroxy-cyclohexyl phenyl ketone (" Irgacure 184 "manufactured by Ciba Specialty Chemicals) (start of radical polymerization) Agent 3 parts by mass, 1 part by mass of 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 9 parts by mass of propoxylated glycerin (“GP-400” produced by Sanyo Chemical Co., Ltd.), pentaerythritol tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] (“Irganox 1010” manufactured by Ciba Specialty Chemicals) and 1 part by mass of distilled water were mixed well to prepare a photocurable resin composition, This was stored in a light-shielded tank.
It was 540 mPa * s when the viscosity of the photocurable resin composition obtained by this was measured by the above-mentioned method.
(Ii) About the photocurable resin composition obtained in the above (i), the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) were determined by the above-described method. Depth (Dp) = 0.07 mm, critical curing energy (Ec) = 14 mJ / cm ² , and working curing energy (E ₁₀ ) = 650 mJ / cm ² .

(2) Manufacture of an optical three-dimensional model for measuring physical properties:
(I) Using the photocurable resin composition prepared in (i) of (1) above, optical three-dimensional modeling is performed in the same manner as (i) of (2) of Example 1 to obtain mechanical properties [ Tensile properties (tensile breaking strength, tensile elongation at break, tensile modulus), yield strength, bending properties (bending strength, bending modulus), impact strength], shrinkage, hardness (Shore D hardness) and heat distortion temperature Each of the optical three-dimensional objects to be manufactured was manufactured, and the obtained optical three-dimensional object (test piece) was irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m ² ) for 20 minutes to be post-cured. .
(Ii) When various physical properties were measured by the above-described method using the optical three-dimensional structure obtained in (i) (post-cured with ultraviolet rays), tensile breaking strength = 26 MPa, tensile breaking elongation = 15.2%, tensile modulus = 1130 MPa, yield strength = 23 MPa, flexural strength = 37 MPa, flexural modulus = 1320 MPa, impact strength = 1.6 kJ / m ² , shrinkage rate = 4.8%, hardness (Shore D hardness) ) = 82 and heat distortion temperature = 35 ° C.

(3) Light irradiation treatment of optical three-dimensional structure:
(I) Using the photocurable resin composition prepared in (i) of (1) above, adopting the same optical modeling conditions as (i) of (2) of Example 1 to create an optical three-dimensional model ( (Vertical x Horizontal x Thickness = 50mm x 30mm x 5mm rectangular parallelepiped) and then UV curing (High pressure mercury lamp) (wavelength 365nm; intensity 30W / m ² ) for 20 minutes did.
The optically three-dimensional modeled article after post-curing with ultraviolet rays thus obtained was almost transparent but yellowed, and the yellowness measured by the above method was 7.0.
(Ii) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional object obtained in (i) above (post-cured by ultraviolet irradiation). The same light source as used in Example 1, which is placed on the upper and lower surfaces and emits blue light (“LP-R5B40” manufactured by LED Paradise, wavelength range of emitted light = 420 to 505 nm, peak wavelength = 455 nm, which does not emit light with a wavelength of 400 nm or less), and each of which is energized with 15 mA, is irradiated with blue-green light from above the optical three-dimensional object for 2 hours. When the yellowness of the optical three-dimensional model was measured by the method described above at the time after irradiation for 2 hours, it was as shown in Table 4 below.
At that time, the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light region), the wavelength range of 380 to 780 nm (visible) on the surface irradiated with the light of the optical three-dimensional object. The integrated value L _A of the relative spectral intensity in the light region) and the integrated value L _B of the relative spectral intensity in the wavelength range of 430 to 500 nm were the same as in Example 1.

Example 8
(1) Preparation of photocurable resin composition:
(I) Hydrogenated bisphenol A diglycidyl ether (50 parts by mass of “HBE-100” manufactured by Shin Nippon Chemical Co., Ltd., 4-phenylthiophenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (“CPI- 200K) (cationic polymerization initiator) 4 parts by mass, dipentaerythritol polyacrylate (“A-9550” manufactured by Shin-Nakamura Chemical Co., Ltd.) 15 parts by mass, 2-hydroxy-2-methyl-1-phenylpropane-1- A photo-curable resin composition obtained by thoroughly mixing 2 parts by mass of ON (“Darocur 1173” manufactured by Ciba Specialty Chemicals) (radical polymerization initiator) and 10 parts by mass of cyclohexanedimethanol (“CHDM” manufactured by Shin Nippon Rika Co., Ltd.) Prepared and housed in a light-tight tank It was.
It was 352 mPa * s when the viscosity of the photocurable resin composition obtained by this was measured by the above-mentioned method.
(Ii) About the photocurable resin composition obtained in the above (i), the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) were determined by the above-described method. Depth (Dp) = 0.39 mm, critical curing energy (Ec) = 26 mJ / cm ² , and working curing energy (E ₁₀ ) = 50 mJ / cm ² .

(2) Light irradiation treatment of optical three-dimensional structure:
(I) Using the photocurable resin composition prepared in (i) of (1) above, adopting the same optical modeling conditions as (i) of (2) of Example 1 to create an optical three-dimensional model ( (Vertical x Horizontal x Thickness = 50mm x 30mm x 5mm rectangular parallelepiped) and then UV curing (High pressure mercury lamp) (wavelength 365nm; intensity 30W / m ² ) for 20 minutes did.
The optically three-dimensional molded article after post-curing with ultraviolet rays obtained in this manner was almost transparent, but yellowed, and the yellowness measured by the method described above was 4.2.
(Ii) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional object obtained in (i) above (post-cured by ultraviolet irradiation). The same light source as used in Example 1, which is placed on the upper and lower surfaces and emits blue light (“LP-R5B40” manufactured by LED Paradise, wavelength range of emitted light = 420 to 505 nm, peak wavelength = 455 nm, which does not emit light with a wavelength of 400 nm or less), and each of which is energized with 15 mA, is irradiated with blue-green light from above the optical three-dimensional object for 2 hours. When the yellowness of the optical three-dimensional model was measured by the method described above at the time after irradiation for 2 hours, it was as shown in Table 4 below.
At that time, the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light region), the wavelength range of 380 to 780 nm (visible) on the surface irradiated with the light of the optical three-dimensional object. The integrated value L _A of the relative spectral intensity in the light region) and the integrated value L _B of the relative spectral intensity in the wavelength range of 430 to 500 nm were the same as in Example 1.

Example 9
(1) Preparation of photocurable resin composition:
(I) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate ("UVR-6105" manufactured by Dow Chemical Company) 50 parts by mass, 3-hydroxymethyl-3-ethyloxetane (manufactured by Toagosei Co., Ltd.) OXT-101 ") 50 parts by mass and 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (" SP-172 "manufactured by ADEKA) (cationic polymerization initiator) ) 3 parts by mass was mixed well to prepare a photocurable resin composition, which was stored in a light-shielded tank.
It was 48 mPa * s when the viscosity of the photocurable resin composition obtained by this was measured by the above-mentioned method.
(Ii) About the photocurable resin composition obtained in the above (i), the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) were determined by the above-described method. Depth (Dp) = 0.10 mm, critical curing energy (Ec) = 12 mJ / cm ² , and work curing energy (E ₁₀ ) = 156 mJ / cm ² .

(2) Light irradiation treatment of optical three-dimensional structure:
(I) Using the photocurable resin composition prepared in (i) of (1) above, adopting the same optical modeling conditions as (i) of (2) of Example 1 to create an optical three-dimensional model ( (Vertical x Horizontal x Thickness = 50mm x 30mm x 5mm rectangular parallelepiped) and then UV curing (High pressure mercury lamp) (wavelength 365nm; intensity 30W / m ² ) for 20 minutes did.
The thus obtained optically three-dimensional model after post-curing with ultraviolet rays had a large degree of yellowing, and the yellowness measured by the above method was 35.4.
(Ii) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional object obtained in (i) above (post-cured by ultraviolet irradiation). The same light source as used in Example 1, which is placed on the upper and lower surfaces and emits blue light (“LP-R5B40” manufactured by LED Paradise, wavelength range of emitted light = 420 to 505 nm, peak wavelength = 455 nm, which does not emit light with a wavelength of 400 nm or less), and each of which is energized with 15 mA, is irradiated with blue-green light from above the optical three-dimensional object for 2 hours. When the yellowness of the optical three-dimensional model was measured by the method described above at the time after irradiation for 2 hours, it was as shown in Table 4 below.
At that time, the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light region), the wavelength range of 380 to 780 nm (visible) on the surface irradiated with the light of the optical three-dimensional object. The integrated value L _A of the relative spectral intensity in the light region) and the integrated value L _B of the relative spectral intensity in the wavelength range of 430 to 500 nm were the same as in Example 1.

Example 10
(1) Preparation of photocurable resin composition:
(I) 8-functional urethane acrylate methacrylate ("N8-231" manufactured by Shin-Nakamura Chemical Co., Ltd .; one obtained by reacting 1 molecule of propoxylated pentaerythritol, 4 molecules of isophorone diisocyanate and 4 molecules of glycerol acrylate methacrylate), acryloyl 25 parts by mass of morpholine (“A-MO” manufactured by Shin-Nakamura Chemical Co., Ltd.), 25 parts by mass of tricyclodecane dimethanol diacrylate (“A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.) and benzyldimethyl ketal (Ciba Specialty) A photo-curable resin composition was prepared by thoroughly mixing 4 parts by mass of “Irgacure 651” (radical polymerization initiator) manufactured by Chemical Co., and this was stored in a light-shielded tank.
It was 540 mPa * s when the viscosity of the photocurable resin composition obtained by this was measured by the above-mentioned method.
(Ii) About the photocurable resin composition obtained in the above (i), the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) were determined by the above-described method. Depth (Dp) = 0.13 mm, critical curing energy (Ec) = 2.8 mJ / cm ² , and working curing energy (E ₁₀ ) = 19.3 mJ / cm ² .

(2) Light irradiation treatment of optical three-dimensional structure:
(I) Using the photocurable resin composition prepared in (i) of (1) above, adopting the same optical modeling conditions as (i) of (2) of Example 1 to create an optical three-dimensional model ( (Vertical x Horizontal x Thickness = 50mm x 30mm x 5mm rectangular parallelepiped) and then UV curing (High pressure mercury lamp) (wavelength 365nm; intensity 30W / m ² ) for 20 minutes did.
The resulting optically three-dimensional modeled article after post-curing with ultraviolet rays had a large degree of yellowing, and the yellowness measured by the method described above was 9.3.
(Ii) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional object obtained in (i) above (post-cured by ultraviolet irradiation). The same light source as used in Example 1, which is placed on the upper and lower surfaces and emits blue light (“LP-R5B40” manufactured by LED Paradise, wavelength range of emitted light = 420 to 505 nm, peak wavelength = 455 nm, which does not emit light with a wavelength of 400 nm or less), and each of which is energized with 15 mA, is irradiated with blue-green light from above the optical three-dimensional object for 2 hours. When the yellowness of the optical three-dimensional model was measured by the method described above at the time after irradiation for 2 hours, it was as shown in Table 4 below.
At that time, the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light region), the wavelength range of 380 to 780 nm (visible) on the surface irradiated with the light of the optical three-dimensional object. The integrated value L _A of the relative spectral intensity in the light region) and the integrated value L _B of the relative spectral intensity in the wavelength range of 430 to 500 nm were the same as in Example 1.

Example 11
(1) Preparation of photocurable resin composition:
(I) 50 parts by mass of tricyclodecane dimethanol dimethacrylate (“DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.), 50 parts by mass of ethoxylated bisphenol A dimethacrylate (“BPE-200” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) (radical polymerization initiator) was mixed well to prepare a photocurable resin composition, which was stored in a light-shielded tank.
It was 320 mPa * s when the viscosity of the photocurable resin composition obtained by this was measured by the above-mentioned method.
(Ii) About the photocurable resin composition obtained in the above (i), the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) were determined by the above-described method. Depth (Dp) = 0.37 mm, critical curing energy (Ec) = 25 mJ / cm ² , and working curing energy (E ₁₀ ) = 49.5 mJ / cm ² .

(2) Light irradiation treatment of optical three-dimensional structure:
(I) Using the photocurable resin composition prepared in (i) of (1) above, adopting the same optical modeling conditions as (i) of (2) of Example 1 to create an optical three-dimensional model ( (Vertical x Horizontal x Thickness = 50mm x 30mm x 5mm rectangular parallelepiped) and then UV curing (High pressure mercury lamp) (wavelength 365nm; intensity 30W / m ² ) for 20 minutes did.
The resulting optically three-dimensional modeled article after post-curing with ultraviolet rays had a high degree of yellowing, and the yellowness measured by the method described above was 61.3.
(Ii) The two-dimensional surface of length × width = 50 mm × 30 mm is placed on a flat table on the yellow-colored optical three-dimensional object obtained in (i) above (post-cured by ultraviolet irradiation). The same light source as used in Example 1, which is placed on the upper and lower surfaces and emits blue light (“LP-R5B40” manufactured by LED Paradise, wavelength range of emitted light = 420 to 505 nm, peak wavelength = 455 nm, which does not emit light with a wavelength of 400 nm or less), and each of which is energized with 15 mA, is irradiated with blue-green light from above the optical three-dimensional object for 2 hours. When the yellowness of the optical three-dimensional model was measured by the method described above at the time after irradiation for 2 hours, it was as shown in Table 4 below.
At that time, the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light region), the wavelength range of 380 to 780 nm (visible) on the surface irradiated with the light of the optical three-dimensional object. The integrated value L _A of the relative spectral intensity in the light region) and the integrated value L _B of the relative spectral intensity in the wavelength range of 430 to 500 nm were the same as in Example 1.

As is clear from the results of Examples 6 to 11 in Table 4 and the results of Examples 1 to 4 in Table 1 above, the wavelength includes light (blue light) having a wavelength in the range of 430 to 500 nm and the wavelength. Irradiates light that does not contain light of 400 nm or less 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 becomes 15 W / m ² or more. The processing method of the present invention that reduces discoloration such as discoloration is the type and component of the resin of the optical three-dimensional model (such as the type of components constituting the photocurable resin composition used for the production of the optical three-dimensional model and Even if the component composition is different, it can be effectively carried out.

<< Reference Example 1 >>
(1) By using the same photocurable resin composition as prepared in (i) of (1) of Example 1, the same optical modeling conditions as in (i) of (2) of Example 1 were adopted. A plurality of optical three-dimensional objects (vertical × horizontal × thickness = 50 mm × 30 mm × 5 mm rectangular parallelepiped) are manufactured, and then these optical three-dimensional objects are irradiated with ultraviolet rays (high pressure mercury lamp) (wavelength 365 nm; intensity 30 W / m). ² ) was post-cured by irradiation for 20 minutes.
All of the optically three-dimensional molded articles after post-curing with ultraviolet rays thus obtained were transparent as a whole, but yellowed, and the yellowness measured by the above-described method was 2.9. .
(2) (i) One of the optical three-dimensional objects obtained by the above (1) (post-cured by ultraviolet irradiation) is in a light-shielded state (after being wrapped in a light-shielding film laminated with aluminum) Stored in a metal can) for 2 days at room temperature, taken out of the can after 2 days, and measured for yellowness by the method described above, and the results were as shown in Table 5 below.
(Ii) In addition, another one of the optical three-dimensional objects obtained by the above (1) (post-cured by irradiation with ultraviolet rays) is the center of the room (the room illuminated with the ultraviolet light cut-off lamp). In addition, it was left as it was for 2 days in an exposed state, and after 2 days, the yellowness was measured by the method described above, and it was as shown in Table 5 below. In the above experiment (ii), the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light range) on the surface of the optical three-dimensional structure left in the room is the method described above. And the integral value L _A of the relative spectral intensity in the wavelength range (visible light range) of 380 to 780 nm on the surface irradiated with the light of the optical three-dimensional object and the wavelength range of 430 to 500 nm. The integral value L _B of the relative spectral intensity is obtained by the method described above, and the light having a wavelength of 430 to 500 nm on the surface irradiated with the light of the optical three-dimensional structure is obtained from the formula: Q × (L _B / L _A ) The total irradiation intensity (W / m ² ) was determined as shown in Table 5 below.
(Iii) Further, another one of the optical three-dimensional objects obtained in the above (1) (post-cured by UV irradiation) is south-facing with sunlight through transparent glass. It was left to stand for 2 days in the state exposed to the window, and after 2 days, the yellowness was measured by the method described above, and it was as shown in Table 5 below. In the experiment of (iii), the total irradiation intensity Q (W / m ² ) in the wavelength range of 380 to 780 nm (visible light region) on the surface of the optical three-dimensional structure left on the window side is as described above. While measuring, the integrated value L _A of the relative spectral intensity in the wavelength range (visible light range) of 380 to 780 nm on the surface irradiated with the light of the optical three-dimensional object and the relative value in the wavelength range of 430 to 500 nm The integral value L _B of the spectral intensity is obtained by the above-described method, and the light having a wavelength of 430 to 500 nm on the surface irradiated with the light of the optical three-dimensional structure is calculated from the formula: Q × (L _B / L _A ). When the total irradiation intensity (W / m ² ) was determined, it was as shown in Table 5 below.

In the case of the above processing method, discoloration such as yellowing that has occurred in the optical three-dimensional object can be easily and easily reduced while maintaining the mechanical properties and other physical properties inherent to the optical three-dimensional object. time quickly eliminated or reduced, or excellent colorless transparency, or one using a coloring agent can be varied in stereolithography product exhibits excellent color tone of the original coloring agents, optical obtained thereby 3D objects include precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, casting models, master models, processing models, complex heat transfer circuits Effective for parts such as parts for design, parts for analysis and planning of heat transfer behavior of complex structures, restoration of artworks, imitation and modern art, art and crafts such as design presentation models for glass-walled buildings It is possible to have.

Claims (3)

An optical three-dimensional object manufactured using a photocurable resin composition, and the spectral transmittance obtained by measuring with a spectrophotometer is numerically calculated by a method prescribed in JIS-K7373, and an auxiliary illuminant C An optical three-dimensional object having a yellowness of 2.4 or less at a thickness of 5 mm obtained under the condition of a visual field of 2 degrees. Light having a wavelength within a range of 430 to 500 nm is applied to an optical three-dimensional object obtained by optical three-dimensional modeling using the photocurable resin composition, and a wavelength of 430 to 400 on the surface of the optical three-dimensional object. The total irradiation intensity of 500 nm light is 15 W / m ² The optical three-dimensional structure according to claim 1, wherein the optical three-dimensional object is obtained by irradiation treatment so as to achieve the above. The optical three-dimensional molded item according to claim 2, wherein the light having a wavelength within a range of 430 to 500 nm is light that does not include light having a wavelength of 400 nm or less.