JP6543498B2 - Manufacturing method of photofabricated article in ink jet photofabrication method - Google Patents

Description

  The present invention relates to a method for producing a photoformed product using an inkjet photofabrication method.

There is widely known a method of producing a three-dimensional design model or a working model by irradiating a liquid photocurable resin with light such as laser light or ultraviolet light to cure it in a predetermined pattern, and producing a liquid photocurable resin. Various resins have been proposed (see, for example, Patent Documents 1 to 6).
In recent years, the optical shaping method by the ink jet method has been proposed, and compared with the conventional method, the liquid photocurable resin discharged from the ink jet nozzle can be cured, laminated and optically shaped, and a large resin as in the prior art There is an advantage that installation of a liquid tank and a dark room becomes unnecessary. Besides being compact and compact in size, the optical forming machine has attracted attention as a 3D CAD that can freely produce a three-dimensional model by using a CAD (Computer Aided Design) system (see, for example, Patent Document 7).

  However, because the heat-resistant temperature is relatively low as it is, a shaped object formed by such a stereolithography method is a component requiring heat resistance, for example, a component around an automobile engine or a component around a lamp such as a copier. It was difficult to apply. When attaching a model of an intake manifold of an automobile engine modeled by stereolithography to the engine and testing the combustion efficiency and intake efficiency of the engine, there is a problem that the model deforms due to heat of the engine with the passage of time. there were. In addition, there is a problem that the warpage after heating is large, and a defect occurs in the dimensional stability.

In addition, technology is developed after shaping to improve heat resistance and suppress the generation of strain with the passage of time, for example, technology to apply (heat) curing promoting energy to a shaped object and cure the uncured liquid It is known (for example, patent document 8).

Unexamined-Japanese-Patent No. 1-204915 JP-A-8-59760 JP-A-9-169827 JP-A-9-316111 JP 2001-310918 A Unexamined-Japanese-Patent No. 2004-59601 Japanese Patent Laid-Open No. 2002-67174 JP 2002-67172 A

  The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method for producing an optical shaped article excellent in heat resistance and mechanical properties.

The present inventors arrived at the present invention as a result of studying to achieve the above object.
That is, the present invention relates to a method for producing an optical formed article using an inkjet optical forming method,
The model material (α) contains a monofunctional ethylenically unsaturated monomer (A), a polyfunctional ethylenically unsaturated monomer (B) and a photopolymerization initiator (C), and from the discharge head for the model material The support material (β) is discharged from the support material discharge head onto the shaping table from the support material discharge head, and the discharged model material (α) is photocured by a photocuring means, and the model material (α) Forming a layer comprising the support material (β) and repeating the process in the height direction to form a laminate (γ) comprising the model material (α) and the support material (β) (I) )When,
And removing a three-dimensional structure (δ) made of the model material (α) as a structure by removing the portion composed of the support material (β) from the laminate (γ), and ,
And (III) removing at least a part of the polyfunctional ethylenically unsaturated monomer (B) as an uncured component in the three-dimensional structure by heating the three-dimensional structure (δ) ,
It is a manufacturing method of the light shaping article characterized by including.

  The optical shaping article manufactured by the manufacturing method of the optical shaping article of the present invention is excellent in heat resistance and mechanical physical properties.

Schematic of inkjet three-dimensional modeling system Side view of a schematic view showing the configuration of a three-dimensional modeling apparatus Plan view of a schematic view showing the configuration of a three-dimensional modeling apparatus Schematic view of one of each printer head from below Schematic of material supply system that supplies model material and support material for each printer head Schematic showing the process of producing a three-dimensional object by operating the three-dimensional object forming apparatus (A) is a schematic view showing a model including a support material for which shaping has been completed, and (B) is a schematic view showing a model in which the support material is removed from the model including the support material for which shaping is completed.

The method for producing an optically shaped product using the inkjet optical shaping method of the present invention discharges the model material (α) from the discharge head for model material and the support material (β) from the discharge head for support material onto the forming table, The discharged model material (α) is photocured by light curing means to form a layer composed of the model material (α) and the support material (β), and this is repeated in the height direction, and the model material (α) Forming a laminate (γ) comprising the support material (β) and the support material (β);
And removing a three-dimensional structure (δ) made of the model material (α) as a structure by removing the portion composed of the support material (β) from the laminate (γ), and ,
Step (III) of removing at least a part of the polyfunctional ethylenically unsaturated monomer (B) as an uncured component in the three-dimensional structure by heating the three-dimensional structure (δ) It consists of three steps.

The model material (α) used in the step (I) which is the first step of the method for producing an optical shaped article using the inkjet optical shaping method of the present invention is a monofunctional ethylenically unsaturated monomer (A), a polyfunctional It is composed of three components of an ethylenically unsaturated monomer (B) and a photopolymerization initiator (C).

The monofunctional ethylenically unsaturated monomer (A) in the present invention is a compound having one ethylenically unsaturated group [such as a (meth) acryloyl group and a vinyl group], and is not particularly limited. As (A), one type may be used alone, or two or more types may be used in combination. Specific examples are shown below.

A linear or branched alkyl (meth) acrylate having 4 to 30 carbon atoms;
[Ethyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, etc. methyl (meth) acrylate, tert-butyl (meth) acrylate, etc.]
(Meth) acrylates having a C6-C20 alicyclic skeleton;
[Cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2 -Methyl-2-ethyl-1,3-dioxolane and adamantyl (meth) acrylate etc.]
(Meth) acrylates having a heterocyclic backbone;
[4- (Meth) acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane etc]
(Meth) acrylates having an aromatic ring having 9 to 15 carbon atoms;
[Phenoxyethyl (meth) acrylate, benzyl (meth) acrylate etc.]
(Meth) acrylate having a hydroxyl group of 5 to 15 carbon atoms;
[Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, etc.]
(Meth) acrylate having a hydroxyl group having a number average molecular weight (hereinafter abbreviated as Mn) of 200 to 2,000;
[Polyethylene glycol (hereinafter abbreviated as PEG) mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polypropylene glycol (hereinafter abbreviated as PPG) mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate and PEG -Mono (meth) acrylate etc of PPG block polymer]
(Meth) acrylamide derivatives having 3 to 15 carbon atoms;
[(Meth) Acrylamide, N-Methyl (Meth) Acrylamide, N-Ethyl (Meth) Acrylamide, N-Propyl (Meth) Acrylamide, N-Butyl (Meth) Acrylamide, N, N'-Dimethyl (Meth) Acrylamide, N , N′-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide and the like].

Among (A), from the viewpoint of the heat resistance of a light-cured product, the glass transition point (hereinafter abbreviated as Tg) of the homopolymer is preferably 80 ° C. or higher, and more preferably 85 to 190 ° C.

  Among (A), preferred is a (meth) acrylate having an alicyclic skeleton having 6 to 20 carbon atoms from the viewpoint of shaping accuracy and heat resistance of a light-cured product, and more preferred is isobornyl (meth) acrylate , Dicyclopentanyl (meth) acrylate and adamantyl (meth) acrylate.

The polyfunctional ethylenically unsaturated monomer (B) in the present invention is a compound having two or more ethylenically unsaturated groups [such as a (meth) acryloyl group and a vinyl group] and is not particularly limited.
As (B), one type may be used alone, or two or more types may be used in combination. Specific examples are shown below.

C5-C30 linear or branched alkylene glycol di, tri or tetra (meth) acrylate;
[Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and trimethylolpropane tetra (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,1 9-nonanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate and 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate etc.]
Di (meth) acrylates having a C 10-30 alicyclic skeleton;
[Dimethylol-tricyclodecanedi (meth) acrylate etc.]
Di (meth) acrylate having an aromatic ring having 10 to 40 carbon atoms;
[Bisphenoxyfluorene (meth) acrylate etc.]
Di (meth) acrylate having a hydroxyl group of Mn 200 to 2,000;
[PEG di (meth) acrylate and PPG di (meth) acrylate etc]
Etc.

In addition, when a bulky methacryl group is contained as (B), since it is possible to raise the Tg while suppressing the cure shrinkage, it is possible to express high heat resistance while suppressing the warpage of the shaped article. From the above, particularly preferred among (B) are polyfunctional ethylenically unsaturated monomers containing a methacryl group in the molecule.

Further, by making (B) a structure having an alicyclic skeleton and / or an aromatic ring described above, there is an effect of expressing high heat resistance while suppressing warpage of a shaped article.
Among the components (B), preferred from the viewpoint of heat resistance are dimethylol-tricyclodecane di (meth) acrylate and bisphenoxyfluorene (meth) acrylate.
Among (B), from the viewpoint of the heat resistance of a light-cured product, the glass transition point (hereinafter referred to as Tg) of the homopolymer is preferably 200 ° C. or higher, more preferably 205 ° C. to 230 ° C., still more preferably It is 210-220 ° C.

  As the polyfunctional ethylenically unsaturated monomer (B) in the present invention, polyfunctional ethylenically unsaturated monomers containing a urethane group in the molecule can also be used, and examples thereof include polyols, organic polyisocyanates and Those formed of (meth) acrylate having a hydroxyl group, or those formed of (meth) acrylate having an organic polyisocyanate and a hydroxyl group, and the like can be mentioned.

  The polyfunctional ethylenically unsaturated monomer (B) in the present invention preferably contains 2 to 6, more preferably 2 to 4 methacryl groups in the molecule from the viewpoint of heat resistance and cure shrinkage. .

Among the components (B), particularly preferred from the viewpoint of heat resistance are dimethylol-tricyclodecane dimethacrylate and bisphenoxyfluorene methacrylate.

As the photopolymerization initiator (C) in the present invention,
Benzoin compound (compound having 14 to 18 carbon atoms);
[Eg benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether etc.]
Acetophenone compound (compound having 8 to 18 carbon atoms);
[Eg acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxy] Acetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one];
Anthraquinone compound (compound having 14 to 19 carbon atoms);
[Eg, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-chloroanthraquinone and 2-amyl anthraquinone]
Thioxanthone compound (compound having 13 to 17 carbon atoms);
[Eg 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone]
Ketal compound (compound having 16 to 17 carbon atoms);
[Eg acetophenone dimethyl ketal and benzyl dimethyl ketal]
Benzophenone compounds (compounds having 13 to 21 carbon atoms);
[Eg benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone]
Phosphine oxide (compound having 22 to 28 carbon atoms);
[Eg, 1,3,5-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis- (2,6-dimethoxy benzoyl) -2,4,4-trimethyl pentyl phosphine oxide and bis ( 2,4,6-trimethyl benzoyl) -phenyl phosphine oxide];
And mixtures thereof.
One of these (C) may be used alone, or two or more may be used in combination.

  Among the above-mentioned (C), acetophenone compounds and phosphine oxides are preferable from the viewpoint of light resistance that the light cured product does not easily turn yellow, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[-] is more preferable. 4- (Methylthio) phenyl] -2-morpholino-propan-1-one, 1,3,5-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide and bis- (2,6-dimethoxy) Benzoyl) -2,4,4-trimethylpentyl phosphine oxide, particularly preferably 1-hydroxycyclohexyl phenyl ketone, 1,3,5-trimethyl benzoyl diphenyl phosphine oxide and 2,4,6-trimethyl benzoyl diphenyl phosphine oxy It is.

The model material (α) in the present invention can optionally contain an additive (D) within the range that does not inhibit the effects of the present invention.
(D) contains a polymerization inhibitor, a colorant, an antioxidant, a chain transfer agent, a filler, etc., and can be selected variously according to the purpose, and one or more of them may be used alone. You may use together.

Production of photofabricated article using three-dimensional modeling system <Step (I)>
FIG. 1 is a schematic view of an inkjet three-dimensional modeling system. As shown in FIG. 1, this system comprises a personal computer (PC) 1 and a three-dimensional modeling apparatus 2 connected to the PC 1. The personal computer 1 receives input of three-dimensional CAD data of an object to be formed, converts the input CAD data as data for three-dimensional formation, for example, into STL (abbreviation of Stereo Lithography) data, and further, this three-order Data of each layer (layer) sliced in the Z direction is generated from the original STL data.

  Specifically, in addition to data of a model material corresponding to a workpiece to be formed, data of a support material for supporting the model material at the time of formation is also generated. Generally, for example, in the Z direction, if the width of the model material at the upper position is larger than the width of the model material at the lower position, and there is a so-called overhang, the software installed in 1 By arranging the support material around the X and Y directions of the lower position model material, the support material is automatically provided so as to support the overhang portion from below.

  Furthermore, 1 also has the function of performing positioning of the three-dimensional data for modeling in the X, Y and Z directions and determination of posture in the modeling space held by the three-dimensional modeling apparatus 2 using STL data. There is. More specifically, while displaying a virtual three-dimensional space in which a modeling space on a modeling table held by the three-dimensional modeling apparatus 2 is three-dimensionally expressed on one screen, at an initial setting position of this space, The three-dimensional STL data of the object to be modeled is displayed, and the three-dimensional STL data of the object to be modeled is held on the screen using a pointing device such as a mouse or a cursor. The desired position and orientation can be determined relative to the build space.

  The three-dimensional modeling apparatus 2 receives the data of each layer (layer) sliced in the Z direction described above from one at a time or in units of each layer, and based on the data of each layer, the three-dimensional modeling apparatus 2 has A two-dimensional printer head is scanned in a main scanning direction (X direction) and a sub scanning direction (Y direction), and a support material is discharged from a printer material discharge printer head from a model material and a support material discharge printer head. To form each layer.

FIG.2 and FIG.3 is schematic which shows the structure of the three-dimensional modeling apparatus 2, FIG. 2 is a side view, FIG. 3 is a top view.
As shown in FIGS. 2 and 3, the three-dimensional modeling apparatus 2 includes a modeling table 21 movable in the Z direction, a printer head 22 for a model material for discharging a model material onto the modeling table, and a printer head 22. A printer head 23 for a support material for discharging a support material onto a modeling table, and an extra model for smoothing the upper surface of a layer discharged from the printer heads 22 and 23 and formed on the modeling table 21 A roller 24 for removing the material and the support material, and a UV light source 25 for photocuring at least the applied model material.

  The above-described printer heads 22 and 23, the roller 24 for smoothing, and the UV light source 25 are positioned and mounted on the printer head module 26, and the main scanning direction above the modeling table 21 by a driving unit (not shown) It is integrally driven in the (X direction) and the sub scanning direction (Y direction).

  FIG. 4 is a schematic view of one of the printer heads 22 and 23 as viewed from below. As shown in FIG. 4, each of the printer heads 22 and 23 is provided at a predetermined interval in the sub scanning direction (Y direction) on the surface facing the modeling table, for discharging a model material and a support material. It has a plurality of orifices.

In FIG. 2, in the case where the model material and the support material are discharged onto the modeling table at least from the printer heads 22 and 23 in the main scanning direction (forward path) moving from left to right, the roller 24 is the right end in the above main scanning direction. The roller rotates in the direction of the arrow shown in FIG. 2, that is, in the clockwise direction.
In other words, the direction in which the printer head module 26 scans when the roller 24 acts and the direction in which the lower portion of the roller 24 rotates (direction of the arrow shown in FIG. 2) are controlled to rotate in the same direction. preferable.

The UV light source 25 extends along the sub-scanning direction, and its length desirably has a length including at least all the orifices provided in each printer head.
Further, as the UV light source 25, it is preferable to use a UV lamp or an LED generally used to cure a photocurable resin.
Further, each time the modeling table 21 forms each layer (layer) based on each slice data corresponding to each layer (layer) by the driving means (not shown), the thickness of each layer is formed prior to the formation of the next layer. Move downward (Z direction) by the minute.

FIG. 5 is a schematic view of a material supply system for supplying model materials and support materials to the respective printer heads 22 and 23.
Cartridges 27 and 28 of a model material and a support material are respectively connected to the respective printer heads 22 and 23, and supply pumps 29 and 30 are respectively provided in the connection path. Each of the cartridges 27 and 28 is replaceable when there is no model material or support material inside.

Next, the three-dimensional modeling method using the three-dimensional modeling system of the inkjet system mentioned above is described.
When CAD data for three-dimensional modeling is input to 1, it is converted into STL data, and on the screen described above, three-dimensional data (model) in the modeling space held by the three-dimensional modeling apparatus 2 After determining the posture of), each slice data in the 1 to Z direction is sent to the three-dimensional modeling apparatus 2.
The three-dimensional modeling apparatus 2 reciprocates the printer head module 26 in the main scanning direction, and during the reciprocation, the model material and the support material are arranged at appropriate positions based on the received slice data. Each layer corresponding to each slice data is stacked on the forming table by controlling the discharge from the step S23.
At least model material is discharged from the printer head 22 to an appropriate position in each layer, and if necessary, the support material is also discharged from the printer head 23 to an appropriate position to form each layer.

Furthermore, for example, when the model material and the support material are discharged from each of the printer heads 22 and 23 in the process of moving the printer head module 26 in the direction from the left to the right (forward path) of FIG. In order to smooth the surface formed from the model material and the support material, the roller 24 has already been applied on the forming table 21 in the process from the left to the left), the model material and the support are removed. While in contact with the surface of the material, it keeps rotating in the above-mentioned rotational direction.
Then, a layer positioned on the uppermost surface formed on the modeling table 21 by irradiating the ultraviolet light from the UV light source 25 mounted on the printer head module 26 to the surface smoothed by the roller 24. To cure the Needless to say, each layer is formed of at least a model material, and a support material is added as needed.
Therefore, each layer is formed by discharging the model material and the support material from each of the printer heads 22 and 23 to form the layer positioned on the top surface of the modeling table 21 and smoothing and smoothing the surface of the layer by the roller 24 The curing of the layer by irradiation of ultraviolet light to the layer located on the top surface of the shaping table 21 is performed, and by repeating these steps, a three-dimensional model is to be shaped.

FIG. 6 is a schematic view showing a three-dimensional shaped object being manufactured by operating the three-dimensional modeling apparatus 2. The part M shown in FIG. 6 is a part on which each layer is laminated by the model material, and the part S is a part on which each layer is laminated by a support material.
As described above, since the model material of the M portion is approximately S-shaped from the lower side to the upper side in the Z direction, in order to support the curved portions in the left and right of the model material shown in FIG. It forms so that a support material may be provided in the part of S.

The inventors of the present application have described the monofunctional ethylenically unsaturated monomer (A) and the polyfunctional ethylenically unsaturated monomer according to the step (I), which is the step of forming a shaped article by the inkjet light shaping method described above. By using a model material containing a monomer (B) and a photopolymerization initiator (C) and prepared so that the target load deflection temperature after shaping becomes 90 to 120 ° C. I formed a shaped object.
And when the load deflection temperature of the modeling thing after modeling was measured, it became clear that load deflection temperature became 50-80 degreeC and did not reach the target load deflection temperature mentioned above.

More specifically, as the monofunctional ethylenically unsaturated monomer (A), a monomer having a homopolymer having a glass transition temperature of 80 ° C. or higher is used, and a polyfunctional ethylenically unsaturated monomer (B )) Using a monomer having a methacryl group in the molecule as well as a homopolymer having a glass transition temperature of 200 ° C. or higher, and further using a model material containing a photopolymerization initiator (C); Although it aimed at the load deflection temperature as a target value after modeling to be 90 to 120 ° C. by the method, it was found that the load deflection temperature was 50 to 80 ° C. and did not reach the target load deflection temperature described above The
Based on this result, the inventors of the present application analyzed the shaped object after completion of shaping, and as a result, the shaped object contains an uncured component, and the presence of this uncured component causes the load of the shaped object It turned out that this is the reason why the deflection temperature did not reach the target value.

  Furthermore, as a result of the inventors examining the cause of causing such a result, the main reason is that the present invention makes the model material compatible with the improvement of the heat resistance and the suppression of the warp of the shaped object. It turned out that it is using the polyfunctional ethylenic unsaturated monomer (B) as a component, and using the inkjet photofabrication method using a model material and a support material as a modeling method.

  Explaining in more detail, the basic aim of the present invention is to improve the heat resistance of the model material while suppressing the warpage of the shaped object, and for the purpose of achieving this aim, a polyfunctional ethylenic non The saturated monomer (B) is used as a component of the model material. However, it has been found that the adoption of the multifunctional ethylenically unsaturated monomer (B), on the other hand, results in a decrease in photocuring reaction performance. More specifically, it is a decrease in photocuring reaction performance with respect to the component of the multifunctional ethylenically unsaturated monomer (B), and in some cases, a part of these polyfunctional ethylenically unsaturated monomers (B) Was found to remain as an uncured component in the shaped article.

<Step (II)>
(A) of FIG. 7 is a schematic view showing a model including the support material completed in this way, and (B) of FIG. 7 removes the support material from the model including the support material completed. Is a schematic view showing a model that has been
As shown in FIG. 7 (A), when modeling of a three-dimensional model is completed by the three-dimensional modeling apparatus 2, a support material for supporting the model material during modeling is integrated with this model. Is formed. For this reason, since this support material is made of a water-soluble material, for example, by immersing it in water, a model (photo-fabricated article) made of only a model material as shown in FIG. Can. Thus, the photofabricated article of the present invention can be obtained.

  In the support material removal described above, the support material is removed by immersion in water, but the support material removal in the present invention is performed by any other method, for example, by separating the model material and the support material by hand. It may be a method of removing material.

<Step (III)>
In step (III), (B) as an uncured component to be removed refers to an unreacted component in the photo-curing reaction of step (I), which usually corresponds to 0.1 to 5% of the total components. .
In addition, when (A) as an uncured component is contained in the three-dimensional structure (δ) after the step (II), at least one of (A) as an uncured component in the step (III) The parts may be removed together.

  Because the presence of (B) as the uncured component in the three-dimensional structure (δ) after step (II) is a factor that reduces the heat resistance of the three-dimensional structure (δ), By removing at least a part of (B) as the uncured component in the step (III), it becomes possible to improve the heat resistance of the three-dimensional structure (δ).

The step of removing the uncured component (III) is carried out for the purpose of removing at least a part of (B) as the uncured component from the three-dimensional shaped object (δ) by heat-treating the three-dimensional shaped object (δ). As a result, the heat resistance is improved.

The heat treatment method in the step of removing the uncured component (III) can be carried out in the atmosphere or by immersion in a solvent, and at least a portion of (B) as an unreacted cured component can be carried out The heat treatment temperature required to remove is preferably 50 to 140 ° C., more preferably 50 to 130 ° C., and still more preferably 50 to 120 ° C.

In the heat treatment method in the step of removing the uncured component (III), at least a part of (B) as the unreacted cured component is efficiently removed, and the heat resistance is improved without deforming the shaped object A preferable method that can be performed is a method in which the heat treatment is performed by being immersed in a solvent.

  In the case of removing at least a part of (B) as an uncured component by immersing the three-dimensional structure (.delta.) In a solvent and performing heat treatment in the removal step (III) of the uncured component, The solubility parameter-(SP) of the solvent used is preferably 8 to 18, more preferably 9 to 16, and further preferably 9 to 14 in order to enhance the compatibility and efficiently perform the removal.

  From the viewpoint of volatility, the boiling point of the solvent used in the removal step (III) of the uncured component is preferably 200 to 500 ° C., more preferably 250 to 500 ° C.

Specific examples of the solvent used in the step of removing the uncured component (III) are shown below. One of these may be used alone, or two or more may be used in combination.
(1) alkylene oxide adduct solvents;
This solvent is obtained by adding an alkylene oxide such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO) to active hydrogen compounds such as water, alcohol, amine and carboxylic acid. It is a solvent obtained by
For example, polyethylene glycol (EO 5 mole adduct of water), propylene glycol (PO 5 mole adduct of water), EO 6 mole adduct of butanol, BO 5 mole adduct of hexanol and the like can be mentioned.
(2) alcohol and ether solvents;
[1,4-butanediol, 1,3-butanediol, 2-ethyl-1-hexanol, benzyl alcohol, butyl carbitol, ethylene glycol, diethylene glycol, triethylene glycol, triethylene glycol monomethyl ether, hexyl glycol, etc.]
(3) hydrocarbon solvents;
[Tarben (solvent naphtha), Solvent # 150 (high-boiling aromatic hydrocarbon), etc.]
(4) ester solvents;
[Carbitol acetate, butyl lactate, methoxybutyl acetate etc.]
(5) silicone oil;
[Dimethyl silicone oil etc.]

  Among these solvents, preferred are alkylene oxide adducts (more preferably polyethylene glycol or polypropylene glycol) from the viewpoint of low volatility and affinity with uncured components in the three-dimensional structure.

It is also possible to perform the removal process (III) of the said unhardened component by heat-processing three-dimensional molded article ((delta)) in air atmosphere, and the heating apparatus to be used in that case is not specifically limited.

The deflection temperature under load of the three-dimensional structure (δ) before heat treatment in the present invention, ie, after step (II) is preferably 50 to 80 ° C., more preferably 55 to 75 ° C. from the viewpoint of heat resistance. More preferably, it is 60-75 ° C.

Further, the deflection temperature under load of the three-dimensional structure (ε) after the heat treatment in the present invention, ie after the step (III) is preferably 90 to 120 ° C., more preferably 92 to 115, from the viewpoint of heat resistance. ° C, more preferably 95 to 110 ° C.

The upper limit of the heating temperature range of the three-dimensional structure in the present invention is equivalent to the final target deflection temperature under load of the three-dimensional structure. Further, even if the heating temperature of the three-dimensional structure in the present invention is below the target deflection temperature, the time required for the heat treatment becomes longer as the temperature is lower, and the heat processing is performed at a temperature slightly lower than the target deflection temperature. In order to show the tendency that the time required for the change hardly changes, it is preferable to experimentally determine in the range of -40.degree. C. from the target load deflection temperature and the load deflection temperature.

After heat treatment in the present invention, that is, the amount of deformation of the three-dimensional structure (ε) after storage in the step (III) (40 ° C. × 10% RH, 24 h) is preferably 1.0 mm from the viewpoint of use It is less than, more preferably less than 0.6 mm.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Unless otherwise stated, parts mean parts by weight and% means weight%.

Production Example 1
In a reaction vessel, 400 parts of PPG (trade name "PPG-400", manufactured by Sanyo Chemical Industries, Ltd., Mn = 400), 524 parts of hydrogenated MDI (dicyclohexylmethane-4,4'-diisocyanate), and a urethanization catalyst 0. 5 parts are charged, reacted at 80 ° C. for 4 hours, then 232 parts of 2-hydroxyethyl acrylate is added, and reacted at 80 ° C. for 8 hours to obtain an ethylenically unsaturated monomer (B-4) having a urethane group. The The functional group number of the obtained ethylenically unsaturated monomer (B-4) having a urethane group was 2, and Mn was 1,388.

Production Example 2
In a reaction vessel, 1,000 parts of PTMG (polytetramethylene ether glycol) (trade name “PTMG-1000, manufactured by Mitsubishi Chemical Co., Ltd., Mn 1,000), 333 parts of IPDI (isophorone diisocyanate) and a urethanization catalyst 0.5 Parts were charged and reacted at 80 ° C. for 4 hours, then 116 parts of 2-hydroxyethyl acrylate was added and reacted at 80 ° C. for 8 hours to obtain an ethylenically unsaturated monomer (B-5) having a urethane group . The functional group number of the obtained ethylenically unsaturated monomer (B-5) having a urethane group was 2, and the Mn was 2,898.

Example 1
The blending composition (parts by weight) of the raw materials of the model material shown in Table 1 was uniformly mixed to obtain a model material (α-1) of Example 1.
Moreover, based on "Example 2-1" of Unexamined-Japanese-Patent No. 2012-111226, the mixing composition (weight part) of the raw material of a support material was mixed uniformly, and the support material ((beta) -1) was obtained.

Subsequently, the model material (α-1) is discharged from the model material discharge head, and the support material (β-1) is discharged from the support material discharge head onto the modeling table at a speed of 20 nL / s. Photocuring is performed by photocuring means with an exposure dose of 300 mJ / cm ² to form a layer consisting of a model material and a support material, and this is repeated in the height direction to obtain a laminate (γ- Obtained 1) (Step I).

A three-dimensional model (δ−) made of the model material is obtained by immersing and removing the portion formed of the support material (β-1) from the laminate (γ-1) in ion exchange water for 24 hours. 1) was taken out as a shaped article (Step II).

Furthermore, the three-dimensional structure shown in Example 1 is obtained by immersing the three-dimensional structure (δ-1) in polyethylene glycol (Mn about 200) (E-1) and heat-treating it at a temperature of 100 ° C. for 24 hours. (Ε-1) was obtained (Step III).

Examples 2 to 8 and Comparative Examples 3 to 4
The same support material (β-1) as in Example 1 is used, and the same process as in Example 1 is performed except for the model material composition (parts), and three-dimensional objects (ε-2) to (ε-) 8) and (ε′-3) to (ε′-4) were obtained.

Example 9
Process treatment was carried out in the same manner as in Example 1 except for the blending ratio of model material (parts by weight) and step III, and in step III, as shown in Table 1, using an air circulation dryer [ESPEC Co., Ltd.] The three-dimensional structure (ε-9) shown in Example 9 was obtained by heat treatment at 100 ° C. for 24 hours in the lower portion.

Comparative Examples 1 and 2
Steps I and II are carried out based on the model material composition (parts by weight) as shown in Table 1, and three-dimensional shaped objects (δ'-1) and (δ'-2) obtained at the end of step II Of (.epsilon .'- 1) and (.epsilon .'- 2) did not carry out the treatment of step III.

The load deflection temperature of the shaped article before and after heat treatment, the breaking strength of the shaped article after heat treatment, the deformation during storage of the shaped article after heat treatment, and the Tg of the shaped article after heat treatment were measured by the following measurement methods.
The results are shown in Table 1.
In Comparative Examples 1 and 2 in which the heat treatment was not performed, the characteristics of the three-dimensional structure obtained at the end of Step II were evaluated. Although "load deflection temperature after heat treatment", "break strength after heat treatment", and "Tg of a shaped article after heat treatment" are shown in Table 1, heat treatment is not performed in Comparative Examples 1 and 2.

In addition, the content which the symbol in Table 1 shows is as follows.
(A-1): Isobornyl acrylate [trade name "light acrylate IBXA" manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups = 1]
(A-2): Isobornyl methacrylate [trade name “Light Ester IB-X”, manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups = 1]
(A-3): 1-adamantyl acrylate [trade name "1-AdA", manufactured by Osaka Organic Chemical Industry Ltd., number of functional groups = 1]

(B-1): dimethylol-tricyclodecane dimethacrylate [trade name "light ester DCP-M", manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups = 2]
(B-2): Bisphenoxyfluorene methacrylate [trade name "BPEF-MA", Shin-Nakamura Chemical Co., Ltd., functional group number 2]
(B-3): dimethylol-tricyclodecane diacrylate [trade name "light acrylate DCP-A", manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups = 2]

(C-1): 1,3,5-trimethyl benzoyl diphenyl phosphine oxide [trade name "Lucirin TPO", manufactured by BASF Corporation]
(C-2): 1-hydroxycyclohexyl phenyl ketone [trade name “IRGACURE 184”, manufactured by Ciba Specialty Chemicals Inc.]
(C-3): bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide [trade name “IRGACURE 819”, manufactured by Ciba Specialty Chemicals Co., Ltd.]

(D-1): Polyether modified polydimethylsiloxane [trade name "BYK 307", manufactured by BIC Chemie Japan Ltd.] (surfactant)
(D-2): hydroquinone monomethyl ether [manufactured by Wako Pure Chemical Industries, Ltd.] (polymerization inhibitor)
(D-3): carbon black [trade name "MHI black # 220, manufactured by Miku country pigment Co., Ltd.]" (coloring agent)

(E-1): polyethylene glycol (Mn about 200) [trade name "PEG 200", manufactured by Sanyo Chemical Industries, Ltd.]
(E-2): Polypropylene glycol (Mn about 400) [trade name "Sannicks PP-400, manufactured by Sanyo Chemical Industries, Ltd."
(E-3): Dimethyl silicone oil [trade name "KF-96", manufactured by Shin-Etsu Chemical Co., Ltd.]

The measurement and evaluation were performed by the following methods. The results are shown in Table 1.
<Method for measuring the deflection temperature under load of a shaped object before heat treatment>
The load deflection temperature is measured according to JIS-K7191 using the load deflection temperature measurement device model number “148-HDPC-3” (manufactured by Yasuda Seiki Co., Ltd.) for the three-dimensional structure (δ) obtained in step II did. The load was high load (1.8 MPa).

<Method of measuring deflection temperature under load of shaped object after heat treatment>
The deflection temperature under load was measured in the same manner as described above for the three-dimensional structure (ε) obtained in step III. The load was high load (1.8 MPa).

<Method of measuring breaking strength (N / mm ² ) of shaped article after heat treatment>
The three-dimensional structure (ε) obtained in step III is pulled at a test speed of 50 mm / min using an autograph [manufactured by Shimadzu Corporation], and the tensile strength at break is measured according to JIS-K7113, It was strength.

<Method of measuring deformation (mm) during storage after heat treatment>
The three-dimensional structure (ε) obtained in step III is molded into a shape of 5 mm in width and 50 mm in length with a cutter to obtain a test piece.
After leaving the test piece horizontally fixed for 24 hours in a constant temperature and humidity chamber (40 ° C., 10% RH), measure the distance from the horizontal surface and the part that hangs down due to deformation due to gravity. mm).

<Method of measuring Tg of shaped article after heat treatment>
A dynamic viscoelasticity measurement (DMA) apparatus [model number “Rheogel-E4000”, using a test piece obtained by forming the three-dimensional structure (ε) obtained in step III into a shape of 5 mm in width and 50 mm in length with a cutter] The Tg was measured at 10 Hz in a tensile mode by the DMA method using U.S. Pat.

  From the results described in Table 1, the three-dimensional structure created by the manufacturing method of the present invention (Examples 1 to 9) is compared to the three-dimensional structure fabricated by the method for comparison (Comparative Examples 1 to 4) It can be understood that the deflection temperature under load is high and the heat resistance is excellent. At the same time, since the breaking strength is also high, it can be seen that the strength as a photofabricated object is sufficiently possessed.

  The three-dimensional object produced by the production method of the present invention has high heat resistance and excellent mechanical properties, so the production method of the present invention is extremely useful as a method for producing an optical shaped article in an inkjet optical shaping method. .

1 Personal computer (PC)
2 3D modeling apparatus 21 Modeling table movable in Z direction 22 Printer head for model material 23 Printer head for support material 24 Roller 25 UV light source 26 Printer head module 27 Cartridge for model material 28 Cartridge for support material 29 For supply Pump 30 Pump for supply

Claims (6)

A method for producing a photoformed product using an inkjet light molding method, comprising:
The model material (α) contains a monofunctional ethylenically unsaturated monomer (A), a polyfunctional ethylenically unsaturated monomer (B) and a photopolymerization initiator (C), and from the discharge head for the model material The support material (β) is discharged from the support material discharge head onto the shaping table from the support material discharge head, and the discharged model material (α) is photocured by a photocuring means, and the model material (α) Forming a layer comprising the support material (β) and repeating the process in the height direction to form a laminate (γ) comprising the model material (α) and the support material (β) (I) )When,
And removing a three-dimensional structure (δ) made of the model material (α) as a structure by removing the portion composed of the support material (β) from the laminate (γ), and ,
And (III) removing at least a part of the polyfunctional ethylenically unsaturated monomer (B) as an uncured component in the three-dimensional structure by heating the three-dimensional structure (δ) ,
Only including,
In the removal process (III) of the said unhardened component, heat processing are performed by being immersed in a solvent, The manufacturing method of the light-shaped article characterized by the above-mentioned.   The method for producing an optical formed article according to claim 1, wherein the heat treatment temperature in the removal step (III) of the uncured component is 50 to 140 ° C. The photoformed article according to claim 1 or 2, wherein the heat treatment is performed by immersing in a solvent having a solubility parameter (SP) of 8 to 18 in the step of removing the uncured component (III). Production method.   The method according to claim 3, wherein the solvent used for immersion in the removal step (III) of the uncured component is an alkylene oxide adduct. The method according to any one of claims 1 to 4 , wherein the load deflection temperature before the heat treatment of the three-dimensional structure is 50 to 80 ° C, and the load deflection temperature after the heat treatment is 90 to 120 ° C. . The method for producing a photoformed article according to any one of claims 1 to 5 , wherein the polyfunctional ethylenically unsaturated monomer (B) contains 2 to 6 methacryl groups in the molecule.

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