JP2001181313A - Optical three-dimensional molding resin composition - Google Patents

Abstract

(57) Abstract: A photocurable resin composition for optical three-dimensional molding capable of producing a three-dimensional molded article excellent in dimensional accuracy and shape stability (particularly in the Z-axis direction) at a high molding speed with high productivity. Provided is an optical three-dimensional molding method using a photocurable resin composition. SOLUTION: A ₁ / A ₀ ≦ 0.95 (where A ₀ indicates the transmittance of curing light in the photo-curable resin composition, and A ₁ indicates the transmittance of the photo-curable resin composition. It shows the transmittance of curing light in the photocured product generated by photocuring.),
Or _{formula; B 1 / B 0 ≦ 0.95} ( wherein, B ₀ represents a transmittance of light having a wavelength of 355nm in the photocurable resin composition, B ₁ is produced by photocuring of the photocurable resin composition The photocurable resin composition for optical three-dimensional modeling that satisfies the transmittance of light having a wavelength of 355 nm in the photocured product thus obtained, and an optical three-dimensional modeling method using the photocurable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition for optical three-dimensional modeling and an optical three-dimensional modeling method using the same. More specifically, the present invention relates to an optical three-dimensional molded article having excellent molding accuracy and dimensional stability, and in particular, a photocuring property capable of producing an optical three-dimensional molded article having excellent Z-axis molding accuracy and excellent dimensional stability. The present invention relates to a resin composition and an optical three-dimensional molding method using the same.

[0002]

2. Description of the Related Art Photocurable resin compositions are widely used as coatings (particularly hard coat agents), photoresists, dental materials, and the like. Recently, photocurable resin compositions based on data input to three-dimensional CAD have been used. A method of three-dimensionally optically forming a conductive resin composition has attracted particular attention. Regarding the optical three-dimensional molding technology, a required amount of controlled light energy is supplied to a liquid photo-curable resin to cure it in a thin layer, and then a liquid photo-curable resin is further supplied thereon, and then the light is controlled under control. A method of producing a three-dimensional object by repeating a process of irradiating and laminating and curing in a thin layer is disclosed in JP-A-56-1.
No. 44478, and its basic practical method was further proposed by JP-A-60-247515. Since then, many proposals have been made regarding optical three-dimensional modeling technology.
966, JP-A-1-204915, JP-A-2-113925, JP-A-2-145616, JP-A-2-153722, JP-A-3-155
No. 20, JP-A-3-21432, JP-A-3-21432.
Japanese Patent No. 41126 discloses a technique relating to an optical three-dimensional printing method.

As a typical method for optically producing a three-dimensional molded article, a computer is controlled so that a desired pattern can be obtained on a liquid surface of a liquid photocurable resin composition placed in a container. Selectively irradiate with ultraviolet laser to cure to a predetermined thickness, then supply one layer of liquid resin composition on the cured layer and irradiate with ultraviolet laser similarly to cure as above There is a method of producing a three-dimensional structure having a final shape by repeating a lamination operation of forming a continuous cured layer. According to this method, a target three-dimensional structure can be easily manufactured in a relatively short time even if the shape of the structure is considerably complicated.

[0004] In recent years, three-dimensional objects obtained by stereolithography have been used from simple concept models to test models, prototypes, and the like. , High modeling accuracy and dimensional stability are increasingly required. In addition, in the optical three-dimensional molding method, it is necessary to improve the reaction rate at the time of stereolithography in order to obtain a target three-dimensional object with high productivity in a short time, and therefore, irradiation of high photopolymerization energy is required. Required. However,
When the energy of the light to be irradiated is high, the penetration depth of the light in the light irradiation direction (Z-axis direction) becomes too high, and the penetration depth of the light in the Z-axis direction tends to be non-uniform. As a result, excessive curing of the resin in the Z-axis direction occurs, the curing state becomes uneven, and the thickness of the cured resin thin layer formed by light irradiation does not become uniform, becomes too thick, or becomes uneven. Therefore, there is a problem that the shaping accuracy (dimensional accuracy) and dimensional stability of a three-dimensional structure formed by stacking a large number of thin layers are reduced, and in particular, the shaping accuracy in the Z-axis direction is significantly reduced.

The above points will be described with reference to the drawings. For example, a three-dimensional structure 1 having a through-hole 2 in the center as shown in FIG. 1A and FIG. 2A is formed by sequentially laminating a liquid photocurable resin composition in a thin layer and photocuring. When the light energy is high and the penetration depth of the light in the Z-axis direction is unnecessarily large when manufacturing by the above-described general-purpose stereolithography technique in which a hardened layer is formed and laminated, the light should be hardened originally. Not only does it reach the photocurable resin composition liquid portion for one layer located on the surface, but also the photocured cured layer located thereunder and the originally photocured under the cured layer The photo-curable resin composition reaches a portion where the photo-curable resin composition is not to be formed, and photo-curing occurs at that portion (excessive curing occurs). As a result, a position indicated by, for example, a dotted line 3 in FIG. 1B and FIG. The photocurable resin composition is cured until the size of the through hole 2 (particularly in the Z-axis direction) Dimension) becomes shorter than the designed, three-dimensional object having a size of the through-hole as designed can not be obtained. In other words, increasing the energy of light to improve the reaction rate during modeling (reducing the modeling time) and the dimensional accuracy and dimensional stability of the three-dimensional model are mutually opposite phenomena. Is difficult.

Under the circumstances described above, high-energy light is irradiated to improve the reaction rate of the resin during molding and shorten the molding time. Investigation and proposals for achieving control and uniformization of the depth of penetration of light in the Z-axis direction into the Z-axis are made from the viewpoints of manufacturing equipment for three-dimensional objects, control methods during light irradiation, composition of photo-curable resin composition, etc. Various things have been done. As a proposal from the material side of the photocurable resin composition regarding the adjustment and uniformity of the penetration of light in the Z-axis direction during light irradiation, the light irradiated in the Z-axis direction is X
A method of adding a deflecting substance capable of deflecting (scattering) in the axis, the Y axis, and other directions to the photocurable resin composition (JP-A-3-15520, JP-A-3-41126)
JP, JP-A-3-1147772, JP-A-3-117732.
No. 114733). However, according to this method, light that has entered the Z-axis direction and has collided with a light deflecting material (light scattering material) is deflected (scattered) beyond a predetermined boundary on a predetermined XY plane of a three-dimensional structure. As a result, it is difficult to control the curing of the resin in the X-axis direction, the Y-axis direction, or other directions perpendicular to the light irradiation direction, and excessive light curing is likely to occur. As a result, the boundary between the light-irradiated part on the XY plane and the part that should not be irradiated with light is blurred, and there is a disadvantage that a three-dimensional structure having a good contour on the XY plane or the like cannot be obtained. . In this method, if the light irradiation is controlled in consideration of the amount of light deflected (scattered) on the XY plane or the like, the control content must be extremely complicated.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to make it possible to smoothly adjust the penetration depth of irradiation light in the Z-axis direction, to prevent excessive hardening in the Z-axis direction, and to further reduce the XY plane. Optical three-dimensional modeling that can smoothly control light curing and produce high-quality optical three-dimensional objects with excellent dimensional accuracy and dimensional stability as a whole at a high modeling speed and with high productivity. To provide a photocurable resin composition for use. Further, an object of the present invention is to provide an optical three-dimensional molding method capable of producing the above-described high-quality optical three-dimensional molded article having excellent dimensional accuracy and dimensional stability at a high molding speed with high productivity. is there.

[0008]

Means for Solving the Problems The inventors of the present invention are originally compatible with each other in that the reaction rate is increased by irradiation with high energy light (that is, the molding time is shortened) and the dimensional accuracy and dimensional stability of the molded object are improved. We have been conducting various studies in search of measures that can satisfy difficult characteristics at the same time. As a result, when photolithography is performed using a photocurable resin composition to which a small amount of a light energy absorber of 0.001 to 1.0% by weight based on the weight of the photocurable resin composition is added, A three-dimensional model that can control the depth of penetration of light in the Z-axis direction without hindering the photoreaction rate (degree of photocurability), and has excellent dimensional accuracy and shape stability at a high modeling speed. In particular, it is possible to obtain high-quality three-dimensional objects with extremely excellent dimensional accuracy and shape stability, especially in the Z-axis direction. In addition, the three-dimensional objects obtained therefrom have excellent mechanical properties such as hardness, tensile strength, and tensile modulus. Was also found to be excellent (Japanese Patent Application Laid-Open No. 8-224790).

The inventors of the present invention conducted further studies based on the above invention, and found that the photocurable resin composition had a light transmittance after photocuring (photocured product) before or after photocuring. When three-dimensional modeling is performed optically using a photocurable resin composition that is lower than the light transmittance of the photocurable resin composition at the time, light in the Z-axis direction can be used even when high-energy light is used. The depth of penetration is smoothly adjusted to prevent excessive curing in the Z-axis direction, and light curing on the XY plane can be smoothly controlled, resulting in excellent overall dimensional accuracy and dimensional stability. It has been found that a high-quality optical three-dimensional object can be manufactured with high productivity at a high molding speed.

Further, the present inventors have found that in such optical three-dimensional modeling, a photocured product having a light transmittance lower than that of a photocurable resin composition before or at the time of photocuring. Any photo-curable resin composition capable of producing a can be used, for example, a component that is converted into a substance that increases the absorptivity of the curing light by irradiation with the curing light, a fluorescent substance that is irradiated with the curing light, It has been found that a photocurable resin composition or the like containing a component that is converted into a substance that generates phenomena is preferably used, and the present invention has been completed based on those findings.

That is, the present invention provides (1) a photocurable resin composition for optical three-dimensional modeling, characterized by satisfying the following mathematical formula:

[0012]

A ₁ / A ₀ ≦ 0.95 (where A ₀ represents the transmittance of curing light in the photocurable resin composition, and A ₁ represents the value obtained by photocuring the photocurable resin composition. It shows the transmittance of curing light in the resulting photocured product.)

Further, the present invention provides (2) a photocurable resin composition for three-dimensional optical molding, characterized by satisfying the following mathematical formula:

[0014]

B ₁ / B ₀ ≦ 0.95 (wherein B ₀ is the wavelength 3 in the photocurable resin composition)
Shows the transmittance of 55nm light, B ₁ wavelength in the light cured material produced by photocuring the photocurable resin composition 355
The light transmittance of nm is shown. ).

In the present invention, (3) the photocurable resin composition is formed by (i) irradiating the surface of the layered photocurable resin composition with light under control so that a predetermined pattern and a predetermined thickness are obtained. And (ii) applying one layer of the photocurable resin composition on the photocurable layer formed in (i) above, and irradiating light under the control to form the photocurable resin composition. ), A light-cured layer having a predetermined pattern and thickness is integrally laminated on the light-cured layer formed in the step (iii), and (iii) the light-cured layer of the above (ii) is formed until a target three-dimensional structure is formed. The photocurable resin composition for optical three-dimensional modeling according to the above (1) or (2), which is used for an optical three-dimensional modeling technique of manufacturing a three-dimensional molded article by repeating a lamination forming step.

Further, the present invention provides (4) a component in which the photocurable resin composition is converted into (a) a substance capable of increasing the absorptivity of curing light upon irradiation with curing light; and (b) )
A photocurable resin composition containing at least one component selected from the group consisting of: a component that is converted into a substance that emits fluorescence upon irradiation with curing light; It is a photocurable resin composition for three-dimensional modeling.

Further, the present invention provides (5) the above (1) to (1).
(4) A method for producing a three-dimensional molded object, comprising using any one of the photocurable resin compositions for optical three-dimensional molding and curing and molding the photocurable resin composition by light irradiation. is there.

Further, according to the present invention, (6) (i) the photocurable resin composition according to any one of the above (1) to (4) is formed into a layer and the surface is irradiated with light under control to obtain a predetermined layer. Forming a photocurable layer having a pattern and thickness, and then (ii) applying one layer of the photocurable resin composition on the photocurable layer formed in (i) and irradiating light under control. Then, a photo-cured layer having a predetermined pattern and thickness is integrally laminated on the photo-cured layer formed in (i), and (iii) the above-mentioned (ii) until a desired three-dimensional structure is formed. (5) The method for producing a three-dimensional structure according to the above (5), which comprises repeating the step of forming a photo-cured layer laminate; and (7) The method according to (5) or (6), wherein the irradiation light is ultraviolet light or light containing ultraviolet light.
And a method for producing a three-dimensional molded article.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the present invention is a photocurable resin composition for optical three-dimensional modeling that satisfies the above-described formula. That is, the photocurable resin composition is applied to a light-transmitting substrate (for example, a glass plate, a light-transmitting plastic sheet, a film, a plate, or the like) to a predetermined thickness and irradiated with curing light from above vertically. light irradiation initial light transmittance of the photocurable resin composition when the (first transmission of the light for curing was irradiated to the light curable resin composition) and a _0, said predetermined subjected on the substrate the light transmittance when irradiated from the vertically upward the light again for a photocurable resin composition having a thickness of the photocured product produced by photocuring light for curing when the a _1, light Ratio A ₁ / A ₀ between light transmittance A ₁ of the cured product and light transmittance A ₀ of the photocurable resin composition.
Is but 0.95 or less (photocured product of the light transmittance A ₁ 95% or less of the light transmittance A ₀ of the photocurable resin composition) optical three-dimensional photo-curable resin composition used for molding a . In the measurement of the light transmittance A ₀ and the light transmittance A ₁ , in order to smoothly adjust the penetration depth of the curing light in the Z-axis direction at the time of actual optical shaping, light is used as the measurement light. The same type of light used for molding and having the same energy intensity is used, and the thickness and the photocuring time of the photocurable resin composition on the light-transmitting substrate are the same as those used for stereolithography. It is desirable to do.

However, the type of light, the energy intensity, the irradiation time, the thickness of one layer of the photocurable resin composition, etc. used in the optical molding are determined by the type and scale of the optical molding apparatus used in the molding, and the manufacturing method. Shape, structure,
Size, since different it may, depending on the type of the photocurable resin composition, the measurement conditions for determining the light transmittance A ₀ and light transmission A ₁ described above there is Kirai difficult determined uniformly. Therefore, in the optical three-dimensional modeling, the photocurable resin composition for optical three-dimensional modeling of the present invention, mainly based on the fact that ultraviolet light or light containing ultraviolet light is widely used, is a light that satisfies the above formula. As a curable resin composition, stereolithography may be performed using a photocurable resin composition that satisfies the formula, and in that case, the penetration depth of light in the Z-axis direction using light having high energy intensity. It is possible to produce a three-dimensional object excellent in dimensional accuracy and dimensional stability in a short molding time and with high productivity while smoothly performing the adjustment of. Therefore, the present invention includes a photocurable resin composition satisfying the above-mentioned formula and an optical three-dimensional molding method using the same.

In the above equation, the light transmittance of B ₁ of the light transmittance of B ₀ and light cured product of the photocurable resin composition when the measurement, a photocurable resin composition light-transmitting substrate (e.g. glass Plate, light-transmitting plastic sheet, film, plate, etc.) to a predetermined thickness (usually 0.1 mm), and irradiate the photocurable resin composition with light having a wavelength of 355 nm from above vertically. The initial light transmittance (transmittance of curing light that was first irradiated on the photocurable resin composition) was B _0, and the photocurable resin composition having the predetermined thickness applied on a substrate was treated with the wavelength of 355 nm. determination of the light transmittance when irradiated again from vertically above the light having a wavelength of 355nm to light cured product produced by photocuring by light as B _1. Light transmittance B ₀
And the light transmittance B ₁ was measured at a wavelength of 355 n
m, the energy intensity is 0.7 mW / cm ²
And the molding time is 1 minute (molding dimension: length x width x thickness = 20mm
× 20 mm × 0.1 mm).

When the photocurable resin composition of the present invention that satisfies the above formula or the above formula is used, the light transmittance of the photocured product is smaller than the light transmittance of the photocurable resin composition before the photocuring. The light-cured material (light-cured layer) once formed has an effect of suppressing light transmission, and excessive light in the Z-axis direction at the portion of the light-cured material (light-cured layer). Is suppressed, light can be prevented from reaching the photocurable resin composition that should not be originally photocured and located further below the photocurable layer, and excessive curing in the Z-axis direction does not occur, A three-dimensional structure excellent in dimensional accuracy and dimensional stability can be obtained. This point will be described with reference to the case of the three-dimensional molded article shown in FIGS. 1 and 2 described above. When the optical molding is performed using the photocurable resin composition of the present invention that satisfies the above-described formula or As shown in FIG. 1B and FIG. 2B, the dimension of the through hole 2 in the Z-axis direction is not reduced, and FIG.
(A) and a three-dimensional structure 1 having a through hole 2 having dimensions as designed as shown in (a) of FIG. 2 (particularly, a three-dimensional structure 1 in which the length of the through hole 2 in the Z-axis direction is as designed) ) Can be manufactured smoothly.

In the photocurable resin composition of the present invention, the value of the above ratio A ₁ / A ₀ or B ₁ / B ₀ between the light transmittance of the photocurable resin composition and the light transmittance of the photocured product. may if 0.95 or less, the lower limit value is not particularly limited, a ₁ / a ₀ or B ₁ / B ₀ of smaller value photocured product of the light in the Z-axis direction by the (photocured layer) The occurrence of excessive intrusion is better prevented, and the dimensional accuracy and dimensional stability of the obtained three-dimensional structure, particularly the dimensional accuracy in the Z-axis direction, are improved. However, in order to increase the interlayer adhesive strength between the photocurable layers and improve the mechanical properties of the three-dimensional structure, the photocurable layer that has already been formed and the photocurable resin composition that has been layered thereon have to be used. because if Write photocuring is slightly generated in the boundary portion is desired also, the value of a ₁ / a ₀ or B ₁ / B ₀ is 0.30 to 0.95
Is preferably, and more preferably 0.50 to 0.90. The photocurable resin composition of the light transmittance and the ratio described above and the light transmittance of the photocured composition A ₁ / A ₀ or B ₁ / B ₀
Is 0.95 or more and does not satisfy the above formula or the above, the photocured product (photocured layer) does not exhibit the action of suppressing or preventing excessive penetration of light in the Z-axis direction, and the dimensional accuracy of the present invention. Can not achieve the purpose.

The photo-curable resin composition of the present invention is a photo-curable resin composition which satisfies the above-mentioned formula or the above-mentioned formula and which can be used for optical three-dimensional molding. The type, the composition of the photocurable resin composition, and the type of the component (additive) contained in the photocurable resin composition are not particularly limited. Although not limited, the photocurable resin composition of the present invention that satisfies the above formulas or (a) is converted into a substance whose absorption rate of curing light is increased by irradiation of curing light. A photocurable resin composition containing at least one component selected from the group consisting of: (b) a component that is converted into a substance that generates fluorescence upon irradiation with curing light; The component (a) and the component (b) may be any of an organic substance, an organometallic compound, an inorganic substance, and a composite thereof, and may be a low molecular substance, an oligomer, a high molecular substance, or a composite of both. It may be.

The photocurable resin composition of the present invention containing the above component (a) which is converted into a substance having an increased absorptivity of the curing light upon irradiation with the curing light, When the object is irradiated with light for curing, a photocured product containing a substance having an increased light absorption rate of the component (a) is formed, and light absorption of the photocured product is caused by the substance in the photocured product. (Light transmission in the photocured product is reduced), whereby the light transmittance of the photocured product is set to 95% or less of the light transmittance of the photocurable resin composition before photocuring (that is, A _1).
/ A ₀ or B ₁ / B ₀ is 0.95 or less).

Examples of the component (a) include: (A) the following general formula (I) by irradiating light such as ultraviolet rays;

[0027]

Embedded image (Wherein, R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent or a phenyl which may have a substituent. A group that can be converted into a benzotriazole-based compound represented by the following formula: X represents a hydrogen atom or a halogen atom (hereinafter referred to as a “benzotriazole precursor”); General formula (II);

[0028]

Embedded image (Wherein, R ³ and R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or phenyl which may have a substituent. A group, a and b each independently represent 0 or 1) (hereinafter referred to as “benzophenone precursor”) which can be converted to a benzophenone-based compound; (C) irradiation with light such as ultraviolet light; The following general formula (III):

[0029]

Embedded image (In the formula, R ⁵ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent or a phenyl group which may have a substituent.) (Hereinafter, referred to as “phenyl salicylate precursor”); (D) irradiation with light such as ultraviolet light, the following general formula (IV):

[0030]

Embedded image (Wherein, R ⁶ and R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent or a phenyl which may have a substituent. Group, R ⁸ has 1 to 20 carbon atoms which may have a substituent.
Is a chain or branched alkyl group. And the like (hereinafter, referred to as “cyanoacrylate precursor”) which can be converted into the cyanoacrylate-based compound represented by the formula (1);

As the component (a), in addition to the above-mentioned compounds, for example, various dyes and their leuco bodies can be exemplified.

In the photocurable resin composition of the present invention containing the above component (b) which is converted into a substance which emits fluorescence by irradiation with curing light, the curing light is applied to the photocurable resin composition. Upon irradiation, a light-cured product containing a substance that emits fluorescence by irradiation with light generated from the component (b) is formed, and particularly when the light-cured product is irradiated with light, the substance generates fluorescence, and the energy of light is increased. Is consumed to generate fluorescence, and as a result, the light energy is reduced, and the light transmittance of the photocured product is reduced to 95% or less of the light transmittance of the photocurable resin composition before photocuring (that is, A ₁ / A ₀ or B ₁ / B ₀ is 0.95
Below). As the component (b), for example, a heterocyclic compound that emits fluorescence when irradiated with light such as ultraviolet light, a substance that is converted into another compound that emits fluorescence, and the like can be given. Specific examples of component (b) include heterocyclic compounds such as oxazine, coumarin, aromatic imide compounds (for example, ethyl imidate derived from 2,3-carboxylic anhydride of naphthalene), benzotriazole derivatives and the like, anthracene , Tetracene, perylene, derivatives thereof (for example, 9,10-diphenylanthracene, rubrene) and the like.

The content of the component (a) and / or component (b) in the photocurable resin composition [component (a)
And when two or more of the components (b) are contained, the total content is used for the types of the components (a) and (b), the type and composition of the photocurable resin composition, and stereolithography. It can be determined according to the type and energy intensity of the curing light, but generally it is about 0.001 to 5.0% by weight based on the total weight of the photocurable resin composition. Preferably, it is about 0.005 to 2.0% by weight, more preferably about 0.01 to 1.0% by weight. If the content of the component (a) and / or the component (b) is too small, it becomes difficult to lower the light transmittance of the photocured product, and the photocurable resin composition satisfying the above formula or It is difficult to obtain. On the other hand, when the content of the component (a) and / or the component (b) is too large, the optical molding speed is reduced, and the mechanical properties of the obtained three-dimensional molded object are easily reduced.

In the present invention, any of the conventionally known liquid photocurable resin compositions for optical three-dimensional molding that can be used for the optical three-dimensional molding technique can be used, and the kind thereof is not particularly limited. However, for example, an acrylate-based photocurable resin composition, a urethane acrylate-based photocurable resin composition, an epoxy-based photocurable resin composition, an epoxy acrylate-based photocurable resin composition, a vinyl ether-based photocurable resin composition Things and the like. These may be used alone or as a mixture. The photocurable resin composition of the present invention, depending on the type of photopolymerizable compound contained in the composition, for example, a photo-radical polymerization initiator,
It contains a photocationic polymerization initiator, or both a photoradical polymerization initiator and a photocationic polymerization initiator.

As the acrylate-based photocurable resin composition, a monofunctional or polyfunctional polyester (meth) acrylate, polyether (meth) acrylate or the like is mainly used, and if necessary, a monofunctional (meth) acrylate monomer, Mix multifunctional (meth) acrylate monomer,
This includes a radical polymerization type liquid photocurable resin composition containing a photoradical polymerization initiator. Examples of the urethane acrylate-based photocurable resin composition include a monofunctional and polyfunctional urethane (meth) acrylate as a main component, and a monofunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer as necessary. Mix,
This includes a radical polymerization type liquid photocurable resin composition containing a photoradical polymerization initiator.

Examples of the epoxy-based photocurable resin composition include one or more of an aliphatic diepoxy compound, an alicyclic diepoxy compound, and an aromatic diepoxy compound. A liquid photocurable resin composition in which a (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer are mixed, and a photocationic polymerization initiator and, if necessary, a photoradical polymerization initiator are contained therein. Examples of the epoxy acrylate-based photocurable resin composition include a monofunctional and polyfunctional epoxy (meth) acrylate as a main component, and a monofunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer as necessary. A liquid photocurable resin composition which is mixed and contains a photoradical polymerization initiator and, if necessary, a photocationic polymerization initiator is exemplified.

Examples of the vinyl ether-based photocurable resin composition mainly include an aliphatic divinyl ether compound, an alicyclic divinyl ether compound, an aromatic divir ether compound and the like, and contain a photoradical polymerization initiator. A liquid photocurable resin composition is exemplified. Further, as examples of the mixed type photocurable resin composition, an acrylate compound,
A mixed liquid photocurable resin composition containing at least two members of a urethane acrylate compound and an epoxy acrylate compound, and further containing a photoradical polymerization initiator and, if necessary, a photocationic polymerization initiator. Can be mentioned.

In particular, in the present invention, the components (a) to (d) described above are used for the urethane acrylate-based photocurable resin composition and / or the epoxy-based photocurable resin composition.
When at least one of these is contained, a three-dimensional molded article having excellent dimensional accuracy and dimensional stability and particularly excellent properties such as mechanical properties can be produced at a high molding speed with good productivity.

The optical three-dimensional modeling resin composition of the present invention comprises:
Leveling agent, surfactant, organic plasticizer,
It may contain an organic filler, an inorganic filler and the like. The preparation method and mixing method of the resin composition for stereolithography of the present invention are not particularly limited, and can be performed according to a conventionally known method.

When performing optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of the present invention, for example, an Ar laser or H laser is used as curing light (active energy ray).
An active energy ray generated from an e-Cd laser, a semiconductor-excited solid-state laser, a xenon lamp, a metal halide lamp, a mercury lamp, a fluorescent lamp, or the like can be used. A particularly preferred active energy ray is a laser beam, and when a laser beam is used, it is possible to improve the modeling accuracy by using its good light-collecting property while increasing the energy level and shortening the modeling time. .

In carrying out the optical three-dimensional molding using the photocurable resin composition of the present invention, any of a conventionally known method and a conventionally known stereolithography system apparatus can be adopted, and there is no particular limitation. Among them, typical examples of the optical three-dimensional molding method preferably used in the present invention include: (i) a layer of the photocurable resin composition of the present invention which is irradiated with light under a controlled pattern to form a predetermined pattern. And forming a photocurable layer having a thickness and then (ii) applying one layer of the photocurable resin composition on the photocurable layer formed in (i) above and irradiating light under control. Then, a photo-cured layer having a predetermined pattern and thickness is integrally laminated on the photo-cured layer formed in (i), and (iii) the above-mentioned (ii) until a desired three-dimensional structure is formed. A method of repeating the photocured layer lamination forming step is preferably employed. The three-dimensional object obtained by this method can be used as it is, or in some cases, post-cured by light irradiation or post-cured by heat, etc., and used after further improving its mechanical properties and shape stability etc. You may do so.

The types of three-dimensional objects manufactured according to the present invention,
The structure, shape, size and the like are not particularly limited, and can be determined according to each use. As the application field of the photocurable resin composition of the present invention, for example, a model for verifying the appearance design during the design, a model for checking the functionality of parts, a resin mold for producing a mold, Examples include a base model for producing a mold, and a direct mold for a prototype mold. More specifically, production of precision parts, electric / electronic parts, furniture, building structures, automobile parts, various containers, castings, molds, models for molds, and models for processing. It is particularly effective in producing models for precision parts that require high dimensional accuracy and good dimensional stability.

[0043]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples. In the following examples, "parts" means parts by weight.

Reference Example 1 [Preparation of urethane acrylate photocurable resin composition] (1) Bisphenol was placed in a 20-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser. 4600 parts of a 4-mol adduct of propylene glycol of A and 4420 parts of isophorone diisocyanate were added thereto, and di-n-butyltin dilaurate was added thereto at 40 to 50 ° C.
6 parts were added and reacted at the same temperature for 30 minutes. Then
After raising the reaction temperature to 80-90 ° C and reacting for 2 hours,
2320 parts of 2-hydroxyethyl acrylate and 5.5 parts of hydroquinone monomethyl ether were added and reacted at the same temperature for another 2 hours to produce a urethane acrylate oligomer having a bisphenol A diol skeleton. (2) 1320 parts of the urethane acrylate oligomer obtained in the above (1), polyethylene glycol 200 diacrylate (“NK ester A-20 manufactured by Shin-Nakamura Chemical Co., Ltd.)
0 ") 1080 parts and ethylene oxide-modified trimethylolpropane triacrylate (" A "manufactured by Shin-Nakamura Chemical Co., Ltd.)
-TMPT-3EO ") was placed in a 5 liter container, and the contents were stirred under reduced pressure and degassed nitrogen for 1 hour at a temperature of 50 ° C for 2 hours. , 2-Dimethoxy-2-phenylacetophenone (“Irgacure 651” manufactured by Ciba Geigy; photoradical polymerization initiator) was added and mixed and stirred at a temperature of 25 ° C. until completely dissolved (mixing time was about 6 hours). Time), a urethane acrylate-based liquid photocurable resin composition was prepared and stored at 25 ° C. while blocking ultraviolet rays.

Reference Example 2 [Preparation of Epoxy-Based Photocurable Resin Composition] (1) A 20-liter four-necked flask equipped with a stirrer, a temperature controller, a thermometer and a condenser was charged with 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 4,000 parts, 1,4-butanediol diglycidyl ether 1,000 parts, 2,2
-Bis [4- (acryloxydiethoxy) phenylpropane ("NK ester A-BPE-" manufactured by Shin-Nakamura Chemical Co., Ltd.)
4 ") 2,500 parts, ethylene oxide-modified trimethylolpropane triacrylate (" A "manufactured by Shin-Nakamura Chemical Co., Ltd.)
-TMPT-3EO ") and add 2,500 parts to add 20 to 2
The mixture was stirred and mixed at a temperature of 5 ° C. for about 1 hour. (2) The mixture obtained in the above (1) (10000 parts)
In an environment where ultraviolet light is blocked, 2,2-dimethoxy-
150 parts of 2-phenylacetophenone (“Irgacure 651” manufactured by Ciba Geigy; photoradical polymerization initiator) and bis [4- (diphenylsulfonio) phenyl]
200 parts of sulfide bishexafluoroantimonate (photocationic polymerization initiator) was added, and the mixture was stirred at a temperature of 25 ° C. until completely dissolved (mixing stirring time: about 6 hours), to thereby obtain an epoxy liquid photocurable resin composition. Was prepared and stored at 25 ° C. under the exclusion of ultraviolet light.

Example 1 (1) To 100 parts of the urethane acrylate liquid photocurable resin composition obtained in Reference Example 1, 0.01 part of rubrene was added, and a uniform liquid was formed at a temperature of 25 ° C. The mixture was sufficiently stirred until a product was obtained, thereby producing a liquid photocurable resin composition for optical three-dimensional modeling. (2) A part of the photocurable resin composition obtained in the above (1) is sampled and applied to a substrate made of a quartz glass plate (1 mm thick) to a thickness of 0.1 mm. Light with a wavelength of 355 nm from above vertically (energy intensity 0.7 mW / cm
² ) was irradiated and the light transmittance B ₀ at the beginning of the irradiation (transmittance of the light that first reached the back surface of the base material) B ₀ was measured. The light transmittance B ₀ was 20%. Further, light having a wavelength of 355 nm (energy intensity: 0.7 mW / cm ² ) was again irradiated from above vertically onto the photocured layer formed by the light irradiation, and the light transmittance was measured as B _1. , 16
%Met. In addition, the molding time at the time of the light irradiation is 1 minute (molding dimension: length × width × thickness = 20 mm × 20 mm × 0.2 mm).
1 mm). From the above results, the light transmittance B _{0 of the} photocurable resin composition obtained in the above (1) before photocuring was obtained.
The ratio B ₁ / B ₀ between the ratio and the light transmittance B ₁ of the photocured product was 0.80.

(3) Using the photocurable resin composition obtained in the above (1), a water-cooled Ar laser beam (“SOLIFORM-500” manufactured by Teijin Seiki Co., Ltd.) using an ultra-high-speed optical molding system (“SOLIFORM-500”). Output 400mW; wavelength 333, 35
1,364 nm) and an irradiation energy of 300 m
Under the condition of W / cm ² , the slice pitch (lamination thickness) is 0.
Stereolithography was performed with an average molding time of 2 mm per layer and 1 mm, and the dimensions of the X-axis x Y-axis x Z-axis were 50 mm x 4 mm x 20
mm, a circular through-hole A with a set diameter of 10.000 mm, a circular through-hole B with a set diameter of 5.000 mm, a circular through-hole C with a set diameter of 4.000 mm, and a set diameter of 3.00.
A three-dimensional structure (a rectangular parallelepiped) shown in FIG. 1 having a circular through-hole D of 0 mm was manufactured. The exposure amount is controlled by SOLI
The normal conditions of the FORM system were used. (4) The dimension (inner diameter) x in the X-axis direction and the dimension (inner diameter) z in the Z-axis direction of each of the through holes A to D in the three-dimensional structure obtained in (3) above are measured, and the ratio between the two is measured. : Z / x was determined, and the roundness of each through-hole was examined. The result was as shown in Table 1 below.

Example 2 (1) 100 parts of the epoxy liquid photocurable resin composition obtained in Reference Example 2 was mixed with ethyl imido acid ester derived from 2,3-carboxylic anhydride of naphthalene. .1 part was added, and the mixture was sufficiently stirred at a temperature of 25 ° C. until a uniform liquid was obtained, to produce a liquid photocurable resin composition for optical three-dimensional modeling. (2) A part of the photocurable resin composition obtained in the above (1) is sampled and applied to a substrate made of a quartz glass plate (1 mm thick) to a thickness of 0.1 mm. Light with a wavelength of 355 nm from above vertically (energy intensity 0.7 mW / cm
² ) was irradiated, and the light transmittance B ₀ at the beginning of the irradiation (transmittance of light that first reached the back surface of the base material) B ₀ was measured. The light transmittance B ₀ was 40%. Further, light having a wavelength of 355 nm (energy intensity: 0.7 mW / cm ² ) was again irradiated from above vertically onto the photocured layer formed by the light irradiation, and the light transmittance was measured as B _1. , 30
%Met. In addition, the molding time at the time of the light irradiation is 1 minute (molding dimension: length × width × thickness = 20 mm × 20 mm × 0.2 mm).
1 mm). From the above results, the light transmittance B _{0 of the} photocurable resin composition obtained in the above (1) before photocuring was obtained.
The ratio B ₁ / B ₀ of the light cured product to the light transmittance B ₁ was 0.75.

(3) Using the photocurable resin composition obtained in (1) above, a three-dimensional structure (rectangular solid) shown in FIG. 1 was produced in the same manner as in Example 1. The exposure amount was controlled under the normal conditions of the SOLIFORM system. (4) The dimension (inner diameter) x in the X-axis direction and the dimension (inner diameter) z in the Z-axis direction of each of the through holes A to D in the three-dimensional structure obtained in (3) above are measured, and the ratio between the two is measured. : Z / x was determined, and the roundness of each through-hole was examined. The result was as shown in Table 1 below.

Comparative Example 1 (1) A part of the photocurable resin composition obtained in Reference Example 1 was sampled and placed on a substrate made of a quartz glass plate (thickness: 1 mm). .1 mm, and light having a wavelength of 355 nm (energy intensity 0.7 mW / c)
m ² ) and the light transmittance at the beginning of the irradiation (the light transmittance of light that first reached the back surface of the substrate) B ₀ was measured.
The transmittance B ₀ was 15%. Further, light having a wavelength of 355 nm (energy intensity: 0.7 mW / cm ² ) was again irradiated from above vertically onto the photocured layer formed by the light irradiation, and the light transmittance was measured as B _1. ,
It was 14.5%. In addition, the molding time at the time of the light irradiation is 1 minute (molding dimension: length × width × thickness = 20 mm × 20 mm ×
0.1 mm). From the above results, the ratio B ₁ / B ₀ of the light transmittance B ₀ of the photo-curable resin composition obtained in the above (1) before light curing to the light transmittance B ₁ of the photo-cured product was 0.1. 97
Met. (2) Using the urethane acrylate-based liquid photocurable resin composition obtained in Reference Example 1, a three-dimensional structure (rectangular parallelepiped) shown in FIG. 1 was produced in the same manner as in Example 1. The exposure amount was controlled under the normal conditions of the SOLIFORM system. (3) The dimension (inner diameter) x in the X-axis direction and the dimension (inner diameter) z in the Z-axis direction of each of the through holes A to D in the three-dimensional structure obtained in (2) above are measured, and the ratio between the two is measured. : Z / x was determined, and the roundness of each through-hole was examined. The result was as shown in Table 1 below.

[0051]

[Table 1]

From the results in Table 1 above, the ratio B ₁ / B ₀ of the transmittance B ₀ of light having a wavelength of 355 nm of the photocurable resin composition to the transmittance B ₁ of light having a wavelength of 355 nm of the photocured product is obtained. Is 0.
In Examples 1 and 2 in which optical three-dimensional modeling was performed using a photocurable resin composition of 95 or less, the penetration depth of light energy in the Z-axis direction could be adjusted well without becoming excessive, Deformation of through-holes A to D in three-dimensional object (particularly Z
It can be seen that a three-dimensional structure having high dimensional accuracy with little (dimension reduction in the axial direction) is obtained. On the other hand, the ratio B ₁ of the transmittance B ₀ of light having a wavelength of 355 nm of the photocurable resin composition to the transmittance B ₁ of light having a wavelength of 355 nm of the photocured product is obtained.
In Comparative Example 1 in which / B ₀ was 0.97 and optical three-dimensional modeling was performed using a photocurable resin composition larger than 0.95, the penetration of light energy in the Z-axis direction was excessive. Therefore, the deformation of the through-holes A to D in the three-dimensional object (particularly, reduction in dimension in the Z-axis direction) is large, and the dimensional accuracy of the obtained three-dimensional object is smaller than that of the three-dimensional object obtained in Example 1 and Example 2. It turns out that it is inferior.

[0053]

According to the present invention, it is possible to obtain an optical three-dimensional structure excellent in dimensional accuracy and shape stability, particularly in dimensional accuracy and shape stability in the Z-axis direction. Moreover,
In the case of the present invention, a three-dimensional structure having excellent dimensional accuracy and dimensional stability, and also excellent in physical properties and mechanical properties represented by hardness, tensile strength, tensile elasticity, etc., using high light energy, It can be manufactured with high productivity in a shortened molding time.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating an example of a three-dimensional structure obtained by performing an optical three-dimensional structure using a photocurable resin composition.

FIG. 2 is a diagram illustrating an example of a three-dimensional structure obtained by performing an optical three-dimensional structure using a photocurable resin composition.

FIG. 3 is a schematic view showing a structure of a three-dimensional structure manufactured in Examples and Comparative Examples in this specification.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Three-dimensional molded item 2 Through hole A Through hole B Through hole C Through hole D Through hole

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F213 AA21E AA36 AA39E AA42E AB04 AP11 AP12 AR12 AR13 WA25 WA32 WA36 WA40 WB01 WL04 WL13 WL23 WL35 WL43 WL92 WW39 4J011 QA05 QA07 QA35 QB14 QB16 QB20 QB24 SA78 SA01 SA01 WA01

Claims (7)

[Claims] 1. A photocurable resin composition for three-dimensional optical molding, characterized by satisfying the following formula: A ₁ / A ₀ ≦ 0.95 (where A ₀ is shows the transmittance of the curing light in the photo-curable resin composition, a ₁ represents a transmittance of the curing light in the optical cured product produced by photocuring the photocurable resin composition.) 2. A photocurable resin composition for optical three-dimensional modeling, characterized by satisfying the following formula: B ₁ / B ₀ ≦ 0.95 (where B ₀ is Wavelength 3 in photocurable resin composition
Shows the transmittance of 55nm light, B ₁ wavelength in the light cured material produced by photocuring the photocurable resin composition 355
The light transmittance of nm is shown. ) 3. The photocurable resin composition, wherein (i) a surface of the layered photocurable resin composition is irradiated with light under control to form a photocurable layer having a predetermined pattern and thickness. And (ii) one layer on the photocured layer formed in (i).
Applying a layer of the photocurable resin composition and irradiating light under control to integrally form a photocurable layer having a predetermined pattern and thickness on the photocurable layer formed in (i), and (Iii) The above (i) until a target three-dimensional structure is formed.
The photocurable resin composition for optical three-dimensional modeling according to claim 1 or 2, which is used for an optical three-dimensional modeling technique of manufacturing a three-dimensional molded article by repeating the step of i) forming a layer of a photocurable layer. 4. A component in which the photocurable resin composition is converted into (a) a substance whose absorption rate of curing light is increased by irradiation with curing light; and (b) a component which is irradiated with curing light. The light for optical three-dimensional modeling according to any one of claims 1 to 3, which is a photocurable resin composition containing at least one component selected from a component that is converted into a substance that generates fluorescence. Curable resin composition. 5. The photocurable resin composition for optical three-dimensional modeling according to claim 1, wherein the photocurable resin composition is cured by light irradiation and molded. A method for producing a three-dimensional structure, characterized by the following. 6. A light having a predetermined pattern and thickness by irradiating the surface of the photocurable resin composition according to any one of claims 1 to 4 in a controlled manner and irradiating the surface with light. Forming a cured layer, and then (ii) applying one layer of the photocurable resin composition on the photocured layer formed in (i) and irradiating light under control to obtain (i) A light curing layer having a predetermined pattern and a thickness is integrally laminated on the light curing layer formed in the above step, and (iii) the light curing layer of the above (ii) is laminated until a target three-dimensional structure is formed. The method for producing a three-dimensional structure according to claim 5, wherein the forming step is repeated. 7. The method for producing a three-dimensional structure according to claim 5, wherein the irradiation light is ultraviolet light or light containing ultraviolet light.