JP2015189942A - Photocurable resin composition, container, solid molding manufacturing installation and manufacturing method of solid molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition improving molding accuracy of optical solid molding in a three-dimensional optical molding of a liquid photocurable resin composition.SOLUTION: A photocurable resin composition comprises: (A) photoinitiator containing acyl phosphine oxide compound; (B) at least one photopolymerizable monomer compound shown in formula B1 and a compound B2; and (C) tertiary organic phosphine compound. (Ends of at least one of Xand Xbond to (α-alkyl) acrylic acid ester group.) B2: (Meta) acrylate having norbornane or norbornene (including derivatives) as a substituent.

Description

  The present invention relates to a photocurable resin composition, a container, a three-dimensional modeled manufacturing apparatus, and a three-dimensional modeled manufacturing method.

  In recent years, a method of three-dimensional optical modeling of a liquid photocurable resin composition based on data input to a three-dimensional CAD has been widely adopted. According to this modeling method, a target three-dimensional model can be manufactured with good dimensional accuracy without producing a mold or the like.

  A resin composition for optical three-dimensional modeling by a surface exposure method containing a dimethacrylate radical polymerizable monomer and an acylphosphine oxide radical polymerization initiator as a photocurable resin composition used in the method for producing such a three-dimensional modeled product. The thing is proposed (patent document 1).

JP 2008-189788 A

  However, in the above-described composition, the radical reaction is difficult to proceed and sufficient modeling accuracy cannot be obtained.

  Then, an object of this invention is to provide the photocurable resin composition used for the optical three-dimensional modeling by the surface exposure system excellent in modeling precision.

式Ｂ１中、
ａは単結合又は二重結合を表し、
Ｒ_１、Ｒ_２、及びＲ_３は、メチル基又は水素原子であり、同一でも異なっても良い。
Ｘ_１及びＸ_２は、それぞれ、下記式Ｂ３で表される置換基又は水素原子であり、同一でも異なっても良い。
Ｘ_１及びＸ_２の少なくとも一方は、下記式Ｂ３で表される置換基である。

式Ｂ３中、
ｂは、単結合又はエーテル結合を表す。
ｎは、０以上の整数である。
Ｒ_７は、Ｃ_ｍＨ_２ｍ＋１で表される置換基であり、ｍは、０以上の整数である。
＊は結合手を表す。

式Ｂ２中、
Ｒ_４、Ｒ_５、及びＲ_６は、メチル基又は水素原子であり、同一でも異なっても良い。
Ｘ_３及びＸ_４は、それぞれ、上記式Ｂ３で表される置換基又は水素原子であり、同一でも異なっても良く、
Ｘ_３及びＸ_４の少なくとも一方は、前記式Ｂ３で表される置換基である。 In order to achieve the object, the photocurable resin composition of the present invention comprises:
It is a photocurable resin composition characterized by including following AC.

A: Photopolymerization initiator B containing acylphosphine oxide compound B: Photopolymerizable monomer compound C: tertiary organic phosphine compound at least one of a compound represented by the following formula B1 and a compound represented by the following formula B2

In Formula B1,
a represents a single bond or a double bond;
R ₁ , R ₂ , and R ₃ are a methyl group or a hydrogen atom, and may be the same or different.
X ₁ and X ₂ are each a substituent represented by the following formula B3 or a hydrogen atom, and may be the same or different.
At least one of X ₁ and X ₂ is a substituent represented by the following formula B3.

In formula B3,
b represents a single bond or an ether bond.
n is an integer of 0 or more.
R ₇ is a substituent represented by C _m H _{2m + 1} , and m is an integer of 0 or more.
* Represents a bond.

In formula B2,
R ₄ , R ₅ , and R ₆ are a methyl group or a hydrogen atom, and may be the same or different.
X ₃ and X ₄ are each a substituent represented by the above formula B3 or a hydrogen atom, and may be the same or different,
At least one of X ₃ and X ₄ is a substituent represented by the formula B3.

  The photocurable resin composition of the present invention can be easily handled because the viscosity of the composition can be lowered by using B as the photopolymerizable monomer compound. Furthermore, since the photocurable resin composition of the present invention can promote radical reaction by using A and C together, high-speed modeling (low-light modeling) is possible. For this reason, the photocurable resin composition of this invention can improve the modeling precision of optical three-dimensional modeling.

FIG. 1 is a cross-sectional view illustrating an example of a configuration of a three-dimensional structure manufacturing apparatus. FIG. 2 is a cross-sectional view illustrating another example of the configuration of the three-dimensional structure manufacturing apparatus.

  The photocurable resin composition of the present invention will be described. As above-mentioned, the photocurable resin composition of this invention is a photocurable resin composition used for the optical three-dimensional modeling by a surface exposure system, Comprising: Said AC.

  As described above, the photocurable resin composition of the present invention is easy to handle because the viscosity of the composition can be lowered by using B as the photopolymerizable monomer compound.

  Moreover, since the photocurable resin composition of this invention can accelerate | stimulate a radical reaction by using said A and said C together, high-speed modeling (low light quantity modeling) is attained. In general, optical three-dimensional modeling by the surface exposure method requires light having a wavelength of 380 nm or less because it is inferior in curability from the ultraviolet region having a wavelength of 380 nm or more to the near ultraviolet region. However, it is difficult to handle light having a wavelength of 380 nm or less. A short wavelength having a wavelength of 380 nm or less is high energy and may cause alteration of the material that is exposed to light. For this reason, in manufacture of the said optical three-dimensional molded item, light shielding with the exterior is needed. In addition, deep polymerization is difficult with light having a wavelength of 380 nm or less. This is because when the wavelength is shortened, light cannot enter in the depth direction of the photo-curing resin, the thickness that can be formed becomes thin, and it takes time for layered modeling. Furthermore, when the coloring material is mixed in the photopolymerization resin, the reflectance and absorption rate of the light are remarkably increased, so that it is difficult to penetrate the shorter wavelength light in the depth direction. On the other hand, the photo-curable resin composition of the present invention containing all of A, B and C has a deep photopolymerization reaction even in the case of relatively low energy near ultraviolet light having a wavelength of 380 nm or more. However, it progresses, sufficient curability is obtained, and furthermore, the molding accuracy of the fine part is excellent.

  For this reason, the photocurable resin composition of this invention can improve the modeling precision of optical three-dimensional modeling.

[Substance A]
In A, the acylphosphine oxide compound is a compound represented by the formula (A).

(R ²⁰ ) ₃ P = O (A)

In formula (A),
Each of the three R ²⁰ is an organic group, and the three R ²⁰ may be the same or different, and at least one R ²⁰ is an acyl group.

In the formula (A), it is preferable that at least one R ²⁰ is a group other than an acyl group. The group other than the acyl group is preferably an aryl group (aromatic group) such as a phenyl group.

式（Ａ１）において、
Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ、直鎖もしくは分岐アルキル基であり、同一でも異なってもよい。
＊は、結合手を表す。
式（Ａ１）で表されるアロイル基は、式（Ａ）中に複数存在する場合は、同一でも異なっていてもよい。 In formula (A), at least one R ²⁰ is preferably an aroyl group (aromatic carbonyl group). The aroyl group is preferably a group represented by the formula (A1).

In formula (A1),
R ²¹ , R ²² and R ²³ are each a linear or branched alkyl group, and may be the same or different.
* Represents a bond.
When a plurality of aroyl groups represented by the formula (A1) are present in the formula (A), they may be the same or different.

In the formula (A1), it is preferable that R ²¹ , R ²² and R ²³ are all methyl groups.

More preferably, the A includes at least one of the compound represented by the formula (A-1) and the compound represented by the formula (A-2).

  A may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include “IRGACURE (registered trademark) 819” and “Lucirin (registered trademark) TPO” manufactured by BASF. One type of A may be used alone, or two or more types may be used in combination.

  The blending amount (A ratio) of A with respect to the total amount of the photocurable resin composition is not particularly limited, and is, for example, 0.1 wt% to 6 wt%. If the A ratio is within the above range, the photocurable resin composition is appropriately cured. Moreover, if the said A ratio is 6 weight% or less, coloring of the three-dimensional molded item by said A will be reduced. The proportion A is preferably 0.5 wt% to 5 wt%, more preferably 1 wt% to 4 wt%.

式Ｂ１中、
ａは単結合又は二重結合を表す。
また、Ｒ_１、Ｒ_２、及びＲ_３は、メチル基又は水素原子であり、同一でも異なっても良い。
また、Ｘ_１及びＸ_２は、それぞれ、下記式Ｂ３で表される置換基又は水素原子であり、同一でも異なっても良い。
また、Ｘ_１及びＸ_２の少なくとも一方は、下記式Ｂ３で表される置換基である。

式Ｂ３中、
ｂは、単結合又はエーテル結合を表す。
また、ｎは、０以上の整数である。
また、Ｒ_７は、Ｃ_ｍＨ_２ｍ＋１で表される置換基であり、ｍは、０以上の整数である。
また、＊は結合手を表す。

式Ｂ２中、
Ｒ_４、Ｒ_５、及びＲ_６は、メチル基又は水素原子であり、同一でも異なっても良い。
また、Ｘ_３及びＸ_４は、それぞれ、上記式Ｂ３で表される置換基又は水素原子であり、同一でも異なっても良い。
また、Ｘ_３及びＸ_４の少なくとも一方は、上記式Ｂ３で表される置換基である。 [Substance B]
The B (photopolymerizable monomer) is at least one photopolymerizable monomer compound of a compound represented by the following formula B1 and a compound represented by the following formula B2.

In Formula B1,
a represents a single bond or a double bond.
R ₁ , R ₂ , and R ₃ are a methyl group or a hydrogen atom, and may be the same or different.
X ₁ and X ₂ are each a substituent or a hydrogen atom represented by the following formula B3, and may be the same or different.
Further, at least one of X ₁ and X ₂ is a substituent represented by the following formula B3.

In formula B3,
b represents a single bond or an ether bond.
N is an integer of 0 or more.
R ₇ is a substituent represented by C _m H _{2m + 1} , and m is an integer of 0 or more.
* Represents a bond.

In formula B2,
R ₄ , R ₅ , and R ₆ are a methyl group or a hydrogen atom, and may be the same or different.
X ₃ and X ₄ are each a substituent or a hydrogen atom represented by the formula B3 and may be the same or different.
At least one of X ₃ and X ₄ is a substituent represented by the above formula B3.

  In the said photocurable resin composition, by containing said B as a photopolymerizable monomer compound, the glass transition point of the said photocurable resin composition becomes high, and a viscosity becomes a moderate thing. Thereby, manufacture of a three-dimensional molded item becomes easy. Specifically, for example, the movement of the work table 21 of the photocurable resin composition when the work table 21 of the three-dimensional object manufacturing apparatus shown in FIGS. 1 and 2 described later is raised or lowered by a predetermined pitch. The followability to a direction improves and the dimensional accuracy of the three-dimensional molded item in the moving direction of the work table 21 improves.

  The glass transition point of the photocurable resin composition is preferably measured at 30 ° C. or more when measured by detecting a thermal change associated with the glass transition of the photocurable resin using a differential scanning calorimeter, More preferably, it is 60 degreeC or more, More preferably, it is 80 degreeC or more.

  The viscosity of the photocurable resin composition was measured using a rotational viscometer at 25 ° C., rotor No. 2, The measured value when measured under the condition of 60 rpm is preferably about 700 mPa · s or less, more preferably 200 mPa · s to 700 mPa · s, and further preferably 230 mPa · s to 370 mPa · s. . When the measured value is about 700 mPa · s or less, the photocurable resin composition is easy to handle. In addition, the liquid followability when moving the stage during modeling is improved, and the liquid level becomes smooth.

In the case where B includes the compound represented by the formula B1, when any _one of the X ₁ and X ₂ is a hydrogen atom, and the B includes the compound represented by the formula B2, It is preferable that either one of X ₃ and X ₄ is a hydrogen atom. Specific examples of the compound include compounds represented by the following formulas B4 to B8. Thereby, since the viscosity of the said photocurable resin composition further falls, handling becomes still easier.

Further, in the formula B3, as represented by the following general formula B9, R ₇ is preferably a methyl group. Thereby, in the radical polymerization reaction in an environment in which oxygen is not present (for example, an environment in which light is irradiated from the lower surface opposite to the upper surface in contact with air), a surplus effect is further reduced and fine modeling is enabled.

  Furthermore, it is preferable that B is a compound represented by the formula B1, and in the formula B1, a is a single bond. Specifically, among the formulas B4 to B8, the compound represented by the formula B6 or B7, in which the a is a single bond, is mentioned. Thereby, the radical generated by the photopolymerization initiator attacks the vinyl group, the photopolymerization reaction easily proceeds, and the curability of the photocurable resin composition is improved. Thereby, a surplus effect is reduced and fine modeling is enabled. Moreover, the hardness of a molded article improves.

  The B is preferably a compound represented by the formula B2. Specific examples of the compound represented by Formula B2 include a compound represented by Formula B8. Thereby, while the viscosity of the said photocurable resin composition further falls, sclerosis | hardenability improves further. Moreover, the hardness of a molded article improves.

  The compound represented by Formula B1 and the compound represented by Formula B2 may be prepared in-house or commercially available products may be used.

Examples of the commercially available compound represented by the formula B1 and a being a double bond include “FA-511AS (R _{1 to} R ₃ : hydrogen atom, X ₁ : hydrogen) manufactured by Hitachi Chemical Co., Ltd. Atom, X ₂ : represented by Formula B3, b is a single bond, n is 0, R ₇ is a hydrogen atom), ”“ FA-512AS (R _{1 to} R ₃ : hydrogen atom, X ₁ : Hydrogen atom, X ₂ : represented by formula B3, b is an ether bond, n is 2, R ₇ is a hydrogen atom) ”,“ FA-512M (R _{1 to} R ₃ : hydrogen atom, X ₁ : hydrogen atom, X ₂ : represented by formula B3, b is an ether bond, n is 2, R ₇ is a methyl group), “FA-512MT (R _{1 to} R ₃ : hydrogen atom, _{X 1:} a hydrogen atom, _{X 2:} represented by formula B3, b is an ether bond, n is 2, _{R 7} is Methyl group) ", and the like.

Further, the formula is represented by B1, and examples of the commercially available products of the compound a is a single bond, for example, Hitachi Chemical Co., Ltd. _{"FA-513M (R 1 ~R 3} : hydrogen _{atom, X} 1: Hydrogen atom, X ₂ : represented by formula B3, b is a single bond, n is 0, R ₇ is a methyl group), “FA-513AS (R _{1 to} R ₃ : hydrogen atom, X ₁ : Hydrogen atom, X ₂ : represented by the formula B3, b is a single bond, n is 0, R ₇ is a hydrogen atom); “DCP (R ₁ to R ₁ -N) manufactured by Shin-Nakamura Chemical Co., Ltd. R ₃ : hydrogen atom, X ₁ and X ₂ : represented by formula B3, b is a single bond, n is 1, R ₇ is a methyl group), “A-DCP (R _{1 to} R ₃ : Hydrogen atom, X ₁ and X ₂ : represented by formula B3, b is a single bond, n is 1, and R ₇ is a hydrogen atom).

Examples of the commercial product of the compound represented by the formula B2 include “Isobonyl acrylate (R _{4 to} R ₆ : methyl group, X ₃ : represented by the formula B3, manufactured by ARK Co., Ltd., and b represents a single bond. N is 0, R ₇ is a hydrogen atom, X ₂ : hydrogen atom, “isobonyl methacrylate (R _{4 to} R ₆ : methyl group, X ₃ : represented by formula B3, b is a single atom A bond, n is 0, and R ₇ is a methyl group, X ₂ : a hydrogen atom) ”or the like.

  The compound represented by the formula B1 and the compound represented by the formula B2 may be used singly or in combination of two or more.

  The blending amount (B ratio) of the B with respect to the total amount of the photocurable resin composition is not particularly limited, and is, for example, 0.1 wt% to 20 wt%, preferably 1.0 wt% to 10 wt%. %, More preferably 2 to 7% by weight. If the said B ratio is 0.1 weight% or more, moderate viscosity will be obtained and the hardness of hardened | cured material will improve. On the other hand, if the B ratio is 20% by weight or less, appropriate dimensional accuracy can be obtained.

式（Ｃ）において、
Ｒ^３１、Ｒ^３２及びＲ^３３は、それぞれ、有機基であり、Ｒ^３１、Ｒ^３２及びＲ^３３は同一でも異なっていてもよい。 [Substance C]
The C (tertiary organic phosphine compound) is a compound represented by the formula (C).

In formula (C):
R ³¹ , R ³² and R ³³ are each an organic group, and R ³¹ , R ³² and R ³³ may be the same or different.

  In the formula (C), the organic group is preferably an aryl group (aromatic group). Thereby, sclerosis | hardenability can be accelerated | stimulated without excessive hardening. The aryl group is preferably a phenyl group. Thereby, curability can be further accelerated without excessive curing. The phenyl group may be substituted or unsubstituted with one or more hydrocarbon groups. The hydrocarbon group is preferably a linear or branched alkyl group, and particularly preferably a methyl group.

In the formula (C), R ³¹ , R ³² and R ³³ are more preferably a phenyl group, an o-tolyl group, an m-tolyl group or a p-tolyl group, respectively.

  More preferably, the C includes a compound represented by the formula (C1). The C is represented by the compound represented by the formula (C-1), the compound represented by the formula (C-2), the compound represented by the formula (C-3), and the formula (C-4). More preferably, it comprises at least one compound selected from the group consisting of compounds. The C particularly preferably includes a compound represented by the formula (C-1). By including the compound represented by the formula (C-1), it is possible to further improve the modeling accuracy such as excessive curing overhang in the warped portion.

式（Ｃ１）において、
Ｒは、水素原子、Ｃ_ｐＨ_２ｐ＋１（ｐは、１〜４の整数）又はＣ_ｑＨ_２ｑ＋１Ｏ（ｑは、１〜４の整数）である。

In the formula (C1),
R is a hydrogen _atom, (the p, 1 to 4 integer) C _{p H 2p +} 1 (the q, 1 to 4 integer) or _C q _{H 2q +} 1 O is.

  C may be prepared in-house or a commercially available product may be used. Examples of the commercially available products include “TOTP (registered trademark) (compound represented by formula (C-1), triorthotolylphosphine)”, “TMTP (registered trademark)” (formula) manufactured by Hokuko Chemical Co., Ltd. (Compound represented by (C-2), trimetatolylphosphine) "," TPTP (registered trademark) (compound represented by formula (C-3), tripalatolylphosphine) "," Hokuko TPP (registered trademark) " (Compound represented by formula (C-4), triphenylphosphine) ”. Furthermore, the compound represented by the formula (D-1) includes “TPAP (registered trademark) (trisparamethoxyphenylphosphine)”, “DPCP (registered trademark) (diphenylcyclohexylphosphine)”, “TCHP (registered trademark)”. (Tricyclohexylphosphine) "," Hokuko TBP (registered trademark) (tri-n-butylphosphine) "," TTBuP (registered trademark) (tritertiary butylphosphine) "," TOCP (registered trademark) (tri-n- Octylphosphine) ”,“ DPPST® (parastyryl diphenylphosphine) ”,“ Amphos ([4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine) ”and“ DPPC® ”. (Diphenylphosphinas chloride) "and the like. C may be used alone or in combination of two or more.

  The blending amount of C with respect to the total amount of the photocurable resin composition is not particularly limited, and is, for example, 0.005 wt% to 0.5 wt%, preferably 0.01 wt% to 0.1 wt%. %, More preferably 0.02 wt% to 0.07 wt%.

  The photocurable resin composition may further contain a conventionally known additive as necessary. Examples of the additive include an ultraviolet absorber.

  The photocurable resin composition can be prepared by, for example, uniformly mixing the A, the B, and the C and, if necessary, other additives by a conventionally known method.

  Next, the container of the present invention will be described. The container of the present invention is a container used for optical three-dimensional modeling by a surface exposure method, and the container contains a photocurable resin composition, and the photocurable resin composition is the photocurable resin of the present invention. It is a composition. Examples of the container of the present invention include a cartridge and a bottle. Since the container of the present invention is filled with the photocurable resin composition, it preferably has light shielding properties.

  Next, the three-dimensional model manufacturing apparatus and the three-dimensional model manufacturing method will be described with examples.

  The three-dimensional object manufacturing apparatus of this example is a three-dimensional object manufacturing apparatus used for optical three-dimensional modeling by a surface exposure method, and the upper opening, or the upper surface or the lower surface has light transmittance, and a photocurable resin inside. A liquid tank filled with the composition; a work table that can move up and down in the liquid tank; and irradiation means for irradiating light on the surface of the photocurable resin composition at the upper or lower part of the liquid tank; The said photocurable resin composition is the photocurable resin composition of this invention, It is characterized by the above-mentioned.

  The manufacturing method of the three-dimensional structure of this example is a manufacturing method of the three-dimensional structure used for the optical three-dimensional structure by a surface exposure system, Comprising: Light is irradiated to the photocurable resin composition of this invention, and a three-dimensional structure is manufactured. It is characterized by manufacturing.

  The manufacturing method of the above-mentioned three-dimensional molded item can be implemented using the above-mentioned three-dimensional molded item manufacturing apparatus, for example.

  In FIG. 1, an example of a structure of the above-mentioned three-dimensional molded item manufacturing apparatus is shown. As shown in FIG. 1, this three-dimensional structure manufacturing apparatus includes a liquid tank 11 in which the photocurable resin composition 12 of the present invention is filled and a photocurable resin composition 12 of the present invention in the liquid tank 11. The main components are a cartridge 30 to be supplied, a workbench 21 that can move up and down in the liquid tank 11, and an irradiation means 15 that irradiates the surface of the photocurable resin composition 12 with light 14 at the bottom of the liquid tank 11. Include as a component. The photocurable resin composition 12 of the present invention is supplied from the cartridge 30 to the liquid tank 11 through a tube 31 having one end connected to the cartridge 30.

  A translucent window 13 made of a translucent plate such as quartz glass is provided on the bottom surface of the liquid tank 11. The irradiation means 15 has a built-in lens for irradiating the light 14 toward the light transmitting window 13. The irradiation unit 15 is connected to the light source 20 through the optical fiber 16 and the optical shutter 18. The irradiating means 15 can be moved in the XY direction in the horizontal plane by the moving means 17 (in FIG. 1, the X direction is the left-right direction and the Y direction is the direction perpendicular to the paper surface). The work table 21 can be moved in the vertical direction by an elevator 22. The moving means 17 and the elevator 22 are controlled by a computer 23.

The manufacture of a three-dimensional structure using the three-dimensional structure manufacturing apparatus shown in FIG. 1 is performed as follows, for example. First, the work table 21 is positioned slightly above the translucent window 13, and the light 14 is scanned along the horizontal cross section of the target three-dimensional object. The amount of the light 14 is not particularly limited, for example, a ^{0.1mW · s / mm 2 ~0.9mW ·} s / mm 2. This scanning is performed by the moving means 17 controlled by the computer 23.

  After irradiating all of one horizontal section (a portion corresponding to the bottom surface or the top surface) of the target three-dimensional model with light 14, the work table 21 is raised by a predetermined pitch, and the cured resin layer 24 and the transparent window 13 In between, uncured photocurable resin composition 12 is allowed to flow. Thereafter, the light 14 is irradiated in the same manner as described above. By repeating this operation, a three-dimensional structure is obtained as a multilayer laminate. The three-dimensional molded item manufactured by the photocurable resin composition 12 of the present invention is excellent in modeling accuracy. The three-dimensional model manufacturing apparatus and the three-dimensional model manufacturing method of this example require a small amount of use of the photocurable resin composition 12, and the degree of freedom of the composition is high. Because it sticks, it is suitable for manufacturing small three-dimensional objects. Since the photocurable resin composition 12 of the present invention is excellent in modeling accuracy such as excessive curing overhang in the warped portion, it can be suitably used for manufacturing such a small three-dimensional modeled object.

  In FIG. 2, the other example of a structure of the above-mentioned three-dimensional molded item manufacturing apparatus is shown. In FIG. 2, the same parts as those in FIG. While the three-dimensional object manufacturing apparatus shown in FIG. 1 irradiates light 14 from the bottom side of the liquid tank 11, the three-dimensional object manufacturing apparatus shown in FIG. 2 is a photocurable resin composition 12 of the present invention. The light 14 is irradiated from above the liquid surface 12a. The manufacture of the three-dimensional structure using the three-dimensional structure manufacturing apparatus shown in FIG. 2 is, for example, photocurable so as to have a predetermined thickness between the work table 21 or the cured resin layer 24 on the surface and the liquid surface 12a. After the resin composition 12 is interposed, the work table 21 is lowered by a predetermined pitch after the light 14 is irradiated to form a cured product of one horizontal section of the target three-dimensional modeled object, Other operations are the same as those using the three-dimensional structure manufacturing apparatus shown in FIG. According to the three-dimensional object manufacturing apparatus and the three-dimensional object manufacturing method of this example, a large amount of the photocurable resin composition 12 is required, and a large three-dimensional object can be manufactured although the degree of freedom of the composition is low. is there.

  Although the three-dimensional model manufacturing apparatus shown in FIGS. 1 and 2 and the three-dimensional model manufacturing method using them have been described, the three-dimensional model manufacturing apparatus and the three-dimensional model manufacturing method of this example are described in these examples. It is not limited.

  As described above, the photocurable resin composition of the present invention is excellent in modeling accuracy. The use of the photocurable resin composition of the present invention is not particularly limited, and can be widely applied to optical three-dimensional modeling by various surface exposure methods.

DESCRIPTION OF SYMBOLS 11 Liquid tank 12 Photocurable resin composition 12a Liquid surface 13 Translucent window 14 Light 15 Exposure means 16 Optical fiber 17 Moving means 18 Optical shutter 20 Light source 21 Work table 22 Elevator 23 Computer 24 Cured resin layer 30 Cartridge 31 Tube

Claims (8)

A photocurable resin composition used for optical three-dimensional modeling by a surface exposure method,
The photocurable resin composition characterized by including following AC.

A: Photopolymerization initiator B containing acylphosphine oxide compound B: Photopolymerizable monomer compound C: tertiary organic phosphine compound at least one of a compound represented by the following formula B1 and a compound represented by the following formula B2

In Formula B1,
a represents a single bond or a double bond;
R ₁ , R ₂ , and R ₃ are a methyl group or a hydrogen atom, and may be the same or different.
X ₁ and X ₂ are each a substituent represented by the following formula B3 or a hydrogen atom, and may be the same or different,
At least one of X ₁ and X ₂ is a substituent represented by the following formula B3.

In formula B3,
b represents a single bond or an ether bond.
n is an integer of 0 or more.
R ₇ is a substituent represented by C _m H _{2m + 1} , and m is an integer of 0 or more.
* Represents a bond.

In formula B2,
R ₄ , R ₅ , and R ₆ are a methyl group or a hydrogen atom, and may be the same or different.
X ₃ and X ₄ are each a substituent represented by the above formula B3 or a hydrogen atom, and may be the same or different.
At least one of X ₃ and X ₄ is a substituent represented by the formula B3.
In the case where B includes the compound represented by the formula B1, when any _one of the X ₁ and X ₂ is a hydrogen atom, and the B includes the compound represented by the formula B2, The photocurable resin composition according to claim 1, wherein either one of X ₃ and X ₄ is a hydrogen atom. In the formula B3, according to claim 1 or 2 photocurable resin composition according R ₇ is a methyl group. The B is a compound represented by the formula B1;
The photocurable resin composition according to any one of claims 1 to 3, wherein a is a single bond in the formula B1.   The photocurable resin composition according to any one of claims 1 to 3, wherein the B is a compound represented by the formula B2. A container used for optical three-dimensional modeling by a surface exposure method,
The container includes a photocurable resin composition,
The said photocurable resin composition is a photocurable resin composition as described in any one of Claims 1-5, The container characterized by the above-mentioned. A three-dimensional model manufacturing apparatus used for optical three-dimensional modeling by a surface exposure method,
An upper opening, or a liquid tank in which an upper surface or a lower surface is light transmissive, and is filled with a photocurable resin composition inside;
A worktable that can move up and down in the liquid tank;
In the upper part or the lower part of the liquid tank, a three-dimensional structure manufacturing apparatus including irradiation means for irradiating light on the surface of the photocurable resin composition,
The said photocurable resin composition is the photocurable resin composition as described in any one of Claims 1-5, The three-dimensional molded item manufacturing apparatus characterized by the above-mentioned. A manufacturing method of a three-dimensional object to be used for optical three-dimensional modeling by a surface exposure method,
A method for producing a three-dimensional modeled object, wherein the photocurable resin composition according to any one of claims 1 to 5 is irradiated with light to produce a three-dimensional modeled object.

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