JP7180068B2 - Curable liquid composition, cured product, method for producing cured product, and apparatus for producing cured product - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable composition, a cured product, a method for producing the cured product, and an apparatus for producing the cured product.

In recent years, several methods of forming a cured product as a modeled product with a 3D printer are known. For example, a method is known in which a resin solution as a liquid photocurable resin is cured one by one by an ultraviolet laser and laminated. This is also called an SLA (Stereolithography) method, a stereolithography method, or the like. For example, Patent Documents 1 and 2 are known as apparatuses using the stereolithography method.

For example, Patent Document 3 describes the use of dimethyl acrylate and urethane acrylate as materials used in the resin solution of the stereolithography method. Moreover, Patent Document 4 describes a radiation-curable composition containing a (meth)acrylate compound or a urethane (meth)acrylate compound.

Conventional resin solutions mainly consist of weak materials such as acrylic resins, and the use of thermosetting resins has been desired in order to obtain models with high hardness.
However, when a thermosetting resin is used in stereolithography, the reaction rate is insufficient, and the optimization of curing conditions has not been determined, and it has not been put to practical use.

An object of the present invention is to provide a curable composition from which a cured product having excellent heat resistance and strength can be obtained even when the cured product is formed by a stereolithography method.

In order to solve the above problems, the present invention provides a curable liquid composition polymerized by at least one of an electron beam and an electromagnetic wave, comprising a thermosetting resin precursor, a polymerization initiator, and fibers, The fibers are liquid at 23° C., have a fiber diameter of 2 to 25 μm, a fiber length of 50 μm or more and 300 μm or less , and are contained in a total amount of 20% by mass or more and 60% by mass or less with respect to the curable liquid composition. The thermosetting resin is an unsaturated polyester resin, and the curable liquid composition after curing has a load deflection temperature of 120° C. or higher when a load of 1.8 MPa is applied in the measurement method of JIS K7191. The fiber diameter and fiber length of the fiber represent average values, and the curable liquid composition after curing is measured with a scanning electron microscope (SEM), and the average of five locations It is characterized by being obtained by seeking .

According to the present invention, it is possible to provide a curable composition from which a cured product having excellent heat resistance and strength can be obtained even when the cured product is formed by stereolithography.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram for demonstrating an example of the manufacturing method of the hardened|cured material of this invention. It is a schematic diagram for demonstrating the other example of the manufacturing method of the hardened|cured material of this invention.

Hereinafter, the curable composition, the cured product, the method for producing the cured product, and the apparatus for producing the cured product according to the present invention will be described with reference to the drawings. In addition, the present invention is not limited to the embodiments shown below, and can be changed within the scope of those skilled in the art, such as other embodiments, additions, modifications, deletions, etc. is also included in the scope of the present invention as long as the functions and effects of the present invention are exhibited.

(Curable composition)
The present invention is a curable composition that is polymerized by at least one of an electron beam and an electromagnetic wave, and is characterized by containing a thermosetting resin precursor and a polymerization initiator.

According to the present invention, a cured product having excellent heat resistance and strength can be obtained even when the cured product is formed by stereolithography. In addition, the curable composition of the present invention is particularly suitable for use in stereolithography, making it possible to easily and efficiently produce a complicated and fine cured product.

The curable composition of the present invention is preferably liquid at room temperature, more preferably liquid at 23°C. In this case, it can be used particularly preferably for stereolithographic modeling.

<Thermosetting resin>
The curable composition of the present invention contains a thermosetting resin precursor, and the thermosetting resin is a resin that is cured by an effect reaction when a curing agent is added to the thermosetting precursor and heat is applied. is. The thermosetting resin is preferably one or more selected from phenol resins, unsaturated polyester resins, polyimide resins, epoxy resins, urethane resins, alkyd resins and diallyl phthalate resins.
The thermosetting resin precursor comprises, for example, a monomer, an oligomer, or a mixture of a monomer and an oligomer that is polymerized by at least one of an electron beam and an electromagnetic wave. Acrylic and vinyl monomers may be included in the thermosetting resin precursor to increase curing strength.

The content of the precursor of the thermosetting resin in the curable composition can be changed as appropriate. It is preferably 10 to 80% by mass with respect to the entire curable composition. When fibers and fillers are not contained, the content is preferably 50% by mass or more. In this case, reduction in strength due to dilution or the like can be suppressed.

<Polymerization initiator>
The curable composition of the present invention contains a polymerization initiator. By using a polymerization initiator that absorbs at least one of an electron beam and an electromagnetic wave, the reaction proceeds and the polymerization is extended, thereby solidifying the resin and obtaining a cured product. The polymerization initiator is preferably one or more selected from radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators and photothermal conversion agents.

The content of the polymerization initiator in the curable composition can be changed as appropriate, but is preferably 0.01 to 5% by mass in the curable composition.

<Electron beam, electromagnetic wave>
The curable composition of the present invention is polymerized by at least one of an electron beam and an electromagnetic wave, and the electron beam and the electromagnetic wave can be appropriately changed as required. The electron beam and electromagnetic wave preferably have sufficient intensity to excite the polymerization initiator.
Examples of electron beams and electromagnetic waves in the present invention include ultraviolet (UV) light, semiconductor lasers, DLP (Digital Light Processing, registered trademark) type light sources, and infrared lasers.
The wavelength of the electromagnetic wave is preferably 250-1000 nm. When UV wavelength initiators are used, wavelengths between 250 and 420 nm are preferred, and when infrared laser wavelengths are required, wavelengths between 700 and 900 nm are preferred.
Two or more types of electron beams and electromagnetic waves may be used, and they may be used simultaneously or by switching in order.

<Fiber, Filler>
The curable composition of the present invention preferably further contains fibers (also referred to as fibers) or fillers. By including fibers or fillers, heat resistance and strength can be further improved.

Fibers include glass fibers, carbon fibers, aramid fibers, metal fibers and the like.
Examples of the metal in the metal fiber include aluminum and magnesium.
Examples of fillers include carbon nanotubes, cellulose nanofibers, glass beads, fullerenes, and the like.
In addition to the above, for example, those described in International Publication No. 2008/057844 pamphlet can be used from the viewpoint of improving strength and heat resistance.
These may be used individually by 1 type, and may use 2 or more types together.

Among these, the fiber is preferably one or more selected from glass fiber, carbon fiber, aramid fiber and aluminum fiber from the standpoint of availability and economy.

The content of fibers and fillers can be changed as necessary, but the total content is preferably 5% by mass or more relative to the curable composition. By containing 5% by mass or more, the effect of improving heat resistance and strength can be obtained.

Moreover, the total content of fibers and fillers is preferably 90% by mass or less with respect to the curable composition. In this case, since many fibers or fillers are included, it is possible to prevent difficulty in modeling.

In addition, the total content of fibers and fillers is more preferably 10% by mass or more and 60% by mass or less in consideration of the viscosity of the curable composition. Moreover, in order to further improve the strength of the cured product, it is more preferably 20% by mass or more.

The shape of the fiber can be appropriately changed as required. For example, the fiber diameter is preferably 1 to 30 μm, and the fiber length is preferably 50 μm or more. The fiber diameter and fiber length of the fiber represent average values, and are obtained by measuring the cured product with a scanning electron microscope (SEM) and averaging five points.

The fiber diameter is more preferably 2-25 μm, more preferably 4-15 μm.
The fiber length is more preferably 100 μm or longer, more preferably 300 μm or longer. Although the upper limit of the fiber length is not particularly limited, it is preferably 3000 μm or less.

When the fiber content is within these preferred ranges, the heat resistance and strength of the cured product can be further improved, and the surface roughness of the cured product is approximately the same as that of the cured product without added fibers or fillers. can be

From the viewpoint of improving the adhesion between the fibers and fillers and the resin, a sizing agent may be added and the fibers and fillers may be surface-treated. Among them, fibers and fillers whose surfaces have been hydrophobized are preferably used.

The method of hydrophobizing treatment is not particularly limited, and conventionally known methods can be used. Examples of hydrophobizing agents used for the hydrophobizing treatment include silane coupling agents such as hexamethyldisilazane (HMDS) and dimethyldichlorosilane (DMDS), and silicone oil processing agents such as dimethylsilicone oil and amino-modified silicone oil. etc. Among these, silane coupling agents are preferably used.

<Other ingredients>
The curable composition may contain other components as necessary.
Examples include antifoaming agents, sizing agents, cross-linking agents, viscosity reducing agents, surface treatment agents, plasticizers, smoothing agents, and solvents.

<Application>
The curable composition of the present invention is used for applications such as prototypes of electronic device parts and automobile parts, prototypes for strength tests, and products in small lots used for aerospace and dress-up tools in the automobile industry. It can be suitably used to form an article for. According to the present invention, the strength of the cured product is expected to be superior to that of materials obtained by existing stereolithography methods, so that it can be used as a practical product.

The production speed is considered to be inferior to mass production such as injection molding, but the required production volume can be secured, for example, by mass-producing small flat parts. Another advantage is that it can be used as a mold for injection molding.

Although the curable composition of the present invention is particularly suitable for stereolithography, it can also be used for systems other than stereolithography. For example, use in an ink jet system is conceivable, but it is necessary to consider an ejection mechanism that can correspond to the viscosity of the curable composition and the diameter of the fiber or filler.

(cured product)
The cured product (also referred to as a modeled product) of the present invention is made of the curable composition of the present invention, and can be obtained by irradiating the curable composition with at least one of electron beams and electromagnetic waves and curing the composition. .

The cured product preferably has a load deflection temperature of 60° C. or higher, more preferably 70° C. or higher, and further preferably 80° C. or higher when a load is applied at 1.8 MPa in the measurement method of JIS K7191. preferable. When the preferable range is satisfied, the heat resistance and hardness of the cured product are further improved, the range of use of the cured product is widened, and the product can withstand use as a practical product.

In addition, as a method for producing a cured product, the operation can be changed as appropriate. For example, the entire laminate may be heated after sequentially curing and laminating the curable compositions. By heating the whole, the heat resistance and strength of the cured product are improved.
In the present invention, a cured product having excellent heat resistance and strength is obtained, and it becomes easy to achieve a deflection temperature under load of 60° C. or higher without heating the entire laminate after modeling is completed.

(Method for producing cured product and apparatus for producing cured product)
The method for producing a cured product of the present invention comprises a thin layer forming step of forming a thin layer of a curable composition on or under the stage, and irradiating at least a part of the thin layer with at least one of an electron beam and an electromagnetic wave. and a curing step of curing with a curable composition, and the curable composition is the curable composition of the present invention.
The apparatus for producing a cured product of the present invention comprises thin layer forming means for forming a thin layer of a curable composition on or under the stage, and at least a part of the thin layer is irradiated with at least one of an electron beam and an electromagnetic wave. The curable composition is the curable composition of the present invention.

The thin layer forming step and thin layer forming means can be changed as appropriate. As the method for producing the cured product and the apparatus for producing the cured product of the present invention, a free liquid surface method, a regulated liquid surface method, or the like can be employed. In the free liquid surface method, for example, a stage is placed in a reservoir to which the curable composition is supplied, and the stage is lowered to form a thin layer of the curable composition on the stage. In addition, depending on the viscosity of the curable composition, it may be difficult to form a thin layer flat, and if necessary, a step of leveling the curable composition may be performed. Further, in the liquid surface regulating method, for example, a stage is placed in a storage section to which the curable composition is supplied, and the stage is raised to form a thin layer of the curable composition under the stage.

At least one of an electron beam and an electromagnetic wave can be applied as the curing step and curing means, and can be changed as appropriate. When irradiating electron beams or electromagnetic waves, the irradiation unit that irradiates the electron beams or electromagnetic waves may be moved to a desired position for irradiation, or a certain range may be irradiated all at once. The range of irradiation can be appropriately changed, and the narrower the range of irradiation, the more precise the cured product can be obtained. The electron beam or electromagnetic wave may be applied from above or below the thin layer.

A known device can be used as an embodiment of the device for producing a cured product of the present invention. For example, as the liquid level regulation method described above, a manufacturing apparatus based on the one-dimensional regulation method described in Japanese Patent No. 5774825 can be used, and a manufacturing apparatus based on the two-dimensional regulation method described in Japanese Patent No. 5605589 can be used. .
Although it is not particularly limited, in the present invention, modeling by stereolithography in a one-dimensional regulation method or a two-dimensional regulation method is preferable because high-viscosity materials can be used.

Note that the method of irradiating a desired portion with an electron beam or an electromagnetic wave is not particularly limited, and can be changed as appropriate. For example, the irradiation position may be changed using a galvanomirror or the like, the irradiation unit may be moved to a desired position, or the stage may be moved. Alternatively, a combination of an f-theta lens and a polygon mirror may be used instead of the galvo mirror.

In the present invention, the thin layer forming step and the curing step are repeated a predetermined number of times as necessary to produce a cured product. By repeating the process a predetermined number of times, the cured portion of the curable composition is laminated to obtain a laminate. The reaction may proceed with microwaves or the like while the laminate is being formed, or the modeled article may be heated with an IR heater or the like. Such a laminate may be used as the cured product of the present invention, or a heating step may be performed after the modeled product is completed to heat the entire laminate to obtain a cured product. By heating the whole, the heat resistance and strength of the cured product can be further improved, and the deflection temperature under load can be made higher. However, in the present invention, there is an advantage that good heat resistance and strength can be obtained without performing such an additional heating step at the end.

A step of stirring the curable composition (stirring step) may be performed after preparing the curable composition using various materials and before the thin layer forming step. By stirring, unevenness of each component in the curable composition can be prevented, and a highly precise cured product can be easily obtained. For the stirring step, a method of stirring by vibration using ultrasonic waves may be used.

Since the method for manufacturing a three-dimensional object according to the present invention does not require a mold such as injection molding, it can achieve overwhelming cost reduction and man-hour reduction in trial production and prototype production. In addition, it is possible to obtain an effect that a complicated and fine cured product can be produced simply and efficiently in the stereolithography method.

One embodiment of the method for producing a cured product of the present invention will be described below, but the present invention is not limited thereto. FIG. 1 shows a schematic diagram for explaining the manufacturing method of this embodiment. As shown in FIG. 1A, a thin layer 20 is formed on the stage 10 by a thin layer forming process. Next, as shown in FIG. 1B, a curing step is performed in which at least part of the thin layer 20 is irradiated with electron beams/electromagnetic waves 30 to be cured. As a result, at least a portion of the thin layer 20 is cured to obtain a cured product 40, as shown in FIG. 1(C). After that, other portions of the thin layer 20 are irradiated with an electron beam/electromagnetic wave 30 so as to form a desired shape. The stage 10 is then lowered, if necessary, to form the next thin layer before repeating the curing process.

FIG. 2 shows a schematic diagram for explaining the manufacturing method of another embodiment. As shown in FIG. 2A, a thin layer 20 is formed under the stage 10 by a thin layer forming process. Next, as shown in FIG. 2B, a curing step is performed in which at least part of the thin layer 20 is irradiated with electron beams/electromagnetic waves 30 to be cured. As a result, at least a portion of the thin layer 20 is cured to obtain a cured product 40, as shown in FIG. 2(C). After that, other portions of the thin layer 20 are irradiated with an electron beam/electromagnetic wave 30 so as to form a desired shape. The stage 10 is then raised, if necessary, to form the next thin layer before repeating the curing process.

In addition, according to the present invention, it is possible to manufacture a shaped article even when the viscosity of the curable composition is high. This is because it goes through a process different from the conventional SLA method. For example, a curable composition having a high viscosity can be favorably shaped by performing stirring or the like that is different from the conventional method.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. Examples 1 to 6 and 12 to 15 refer to Reference Examples 1 to 6 and 12 to 15, which are not included in the present invention.

(Example 1)
<Preparation of curable composition>
A curable composition was prepared with the following composition. The resulting curable composition was liquid at 23°C (the same applies to other examples). In addition, hereinafter, "resin" in the curable composition represents a precursor (monomer) of the resin (the same applies to other examples).

Unsaturated polyester resin (LP-921-N manufactured by DIC) 99.5% by mass
Radical polymerization initiator 1 (irgacure 1173 manufactured by BASF) ... 0.3% by mass
Defoamer (RS-408 manufactured by DIC) 0.2% by mass

<Production of cured product>
028J manufactured by DWS was additionally improved so that it could be irradiated with a semiconductor laser of 806 nm after being irradiated with a normal laser light source. It should be noted that ordinary laser light sources and semiconductor lasers correspond to the electromagnetic waves referred to in the present invention.
100 g of the curable composition obtained above was weighed, and a shaped product (cured product) was produced using the improved apparatus with a lamination pitch of 50 μm. After thoroughly washing the obtained shaped article with ethanol, it was allowed to air dry. As for the shaped article, three test pieces described in JIS K7191 were prepared so that the Z-axis direction was the longest side.

(Example 2)
A curable composition was produced with the following composition, and a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

Unsaturated polyester resin (LP-921-N manufactured by DIC) 99.5% by mass
Photothermal conversion agent 1 (IR-806 manufactured by SigmaAldrich) 0.3% by mass
Defoamer (RS-408 manufactured by DIC) 0.2% by mass

(Example 3)
A curable composition was produced with the following composition, and a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

Polyamic acid (UPIA AT manufactured by Ube Corporation) 99.4% by mass
Anionic initiator 1: 0.2% by mass
(2-(9-Oxoxanthen-2-yl)propionic Acid 1,5,7-Triazabicyclo[4.4.0]dec-5-ene Salt (manufactured by TCI))
Photothermal conversion agent 1 (IR-806 manufactured by SigmaAldrich) 0.2% by mass
Defoamer (RS-408 manufactured by DIC) 0.2% by mass

(Example 4)
A curable composition was prepared with the following composition, and a modeled object was produced in the same manner as in Example 1 except that the obtained curable composition was irradiated with an electron beam (0.1 Gy, manufactured by Eye Electron Beam). made.

Liquid epoxy resin (DIC EPICLON EXA-4850) 49.6% by mass
Liquid epoxy resin (EPICLON HP-4710 manufactured by DIC) 49.7% by mass
Cationic initiator 1 (ADEKA Arkles SP-170) 0.3% by mass
Photothermal conversion agent 1 (IR-806 manufactured by SigmaAldrich) 0.2% by mass
Defoamer (RS-408 manufactured by DIC) 0.2% by mass

(Example 5)
A curable composition was produced with the following composition, and a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

Liquid epoxy resin (DIC EPICLON EXA-4850) 49.6% by mass
Liquid epoxy resin (EPICLON HP-4710 manufactured by DIC) 49.7% by mass
Anionic initiator 1: 0.3% by mass
(2-(9-Oxoxanthen-2-yl)propionic Acid 1,5,7-Triazabicyclo[4.4.0]dec-5-ene Salt (manufactured by TCI)
Photothermal conversion agent 1 (IR-806 manufactured by SigmaAldrich) 0.2% by mass
Defoamer (RS-408 manufactured by DIC) 0.2% by mass

(Example 6)
A curable composition was produced with the following composition, and a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

Phenolic resin (EPICLON EXA-4850 manufactured by DIC) 49.6% by mass
Liquid epoxy resin (EPICLON HP-4710 manufactured by DIC) 49.7% by mass
Cationic initiator 1 (ADEKA Arkles SP-170) 0.2% by mass
Photothermal conversion agent 1 (IR-806 manufactured by SigmaAldrich) 0.2% by mass
Anionic initiator 1: 0.1% by mass
(2-(9-Oxoxanthen-2-yl)propionic Acid 1,5,7-Triazabicyclo[4.4.0]dec-5-ene Salt (manufactured by TCI)
Defoamer (RS-408 manufactured by DIC) 0.2% by mass

(Example 7)
Glass fiber (SS05-413 manufactured by Nitto Boseki Co., Ltd., hereinafter referred to as "GF1") was added to the curable composition of Example 1 in an amount of 20% by mass relative to the entire curable composition, and Mazemazeman (manufactured by MISUGI Co., Ltd.) was added. and stirred for 10 minutes. Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Example 8)
Carbon fiber (M-2007S manufactured by Kreca Co., hereinafter referred to as "CF") was added to the curable composition of Example 1 in an amount of 20% by mass with respect to the entire curable composition, and photothermal conversion was performed instead of the radical polymerization initiator. Agent 1 (IR-806 manufactured by SigmaAldrich) was added and stirred for 10 minutes with a Mixing Man (manufactured by MISUGI). Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Example 9)
Add 20% by mass of aramid fiber (manufactured by Teijin, hereinafter referred to as "AF") to the curable composition of Example 1 with respect to the entire curable composition, and stir for 10 minutes with a Mixing Man (manufactured by MISUGI). did. Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Example 10)
Aluminum fiber (manufactured by Alumina Seven Co., hereinafter referred to as "AlF") was added to the curable composition of Example 1 in an amount of 20% by mass with respect to the entire curable composition, and photothermal conversion agent 1 was used instead of the radical polymerization initiator. (IR-806 manufactured by SigmaAldrich) was added and stirred for 10 minutes with a Maze-Maze Man (manufactured by MISUGI). Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Example 11)
To the curable composition of Example 1, 40% by mass of glass fiber (manufactured by Nitto Boseki Co., Ltd., hereinafter referred to as "GF2") having a different fiber length from GF1 was added to the entire curable composition, and a mixing man was added. (manufactured by MISUGI) and stirred for 10 minutes. Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Example 12)
A curable composition was produced by replacing the unsaturated polyester resin in Example 2 with the polyamic acid (Upia AT manufactured by Ube Corporation) of Example 3. Next, 20% by mass of glass fiber (manufactured by Nitto Boseki Co., Ltd., "GF2") was added to the resulting curable composition, and the mixture was stirred for 10 minutes with a Mixing Man (manufactured by MISUGI). Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Example 13)
In Example 11, the unsaturated polyester resin was replaced with an alkyd resin (manufactured by Arakawa Chemical Co., Ltd.) raw material. Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Example 14)
In Example 11, the unsaturated polyester resin was replaced with a diallyl phthalate resin (manufactured by Sumitomo Bakelite Co., Ltd.). Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Example 15)
In Example 11, instead of the unsaturated polyester resin, urethane acrylate resin (CBZ500LM-AS manufactured by Nippon U-Pica Co., Ltd.) and urethane resin (Takenate 500 manufactured by Mitsui Chemicals, Inc.) raw materials were substituted so that the weight ratio was 1:1. . In addition, 0.15% by mass of the radical polymerization initiator 1 and 0.15% by mass of the photothermal conversion agent 1 were added. Thus, a curable composition of this example was obtained. Next, a shaped article was produced in the same manner as in Example 1 using the obtained curable composition.

(Comparative example 1)
Modeling was carried out in the same manner as in Example 1, except that the radical polymerization initiator 1 was not added. However, the model could not be produced.

(Comparative example 2)
In Example 1, modeling was performed in the same manner as in Example 1, except that alpha rays were irradiated instead of electromagnetic wave irradiation. However, the molding was not possible.

(Comparative Example 3)
Modeling was carried out in the same manner as in Example 3, except that the anionic initiator 1 and the photothermal conversion agent 1 were not added. However, the model could not be produced.

(Comparative Example 4)
In Example 4, modeling was performed in the same manner as in Example 4, except that anionic initiator 1 and photothermal conversion agent 1 were not added. However, the model could not be produced.

(Comparative Example 5)
Modeling was carried out in the same manner as in Example 6, except that the cationic initiator 1, the photothermal conversion agent 1 and the anionic initiator 1 were not added. However, the model could not be produced.

(Comparative Example 6)
Modeling was carried out in the same manner as in Example 1, except that the unsaturated polyester resin was changed to hydroxyethylacrylamide (manufactured by KJ Chemicals).

(Comparative Example 7)
In Comparative Example 6, 10% by mass of a glass fiber (manufactured by Nitto Boseki Co., Ltd., hereinafter referred to as "GF3") having a different fiber diameter and fiber length from GF1 was added to the entire curable composition, and Mazemazeman (MISUGI Modeling was carried out in the same manner as in Comparative Example 6, except that the mixture was stirred for 10 minutes.

(evaluation)
Of the examples and comparative examples, the molded products were subjected to a deflection test under load according to JIS K7191. A HOT TESTER 3M-2 manufactured by Toyo Seiki Co., Ltd. was used as the measuring device, and the test was performed by a flatwise method with a load of 1.8 MPa, and the temperature when the load changed by 0.34 mm was taken as the deflection temperature under load. A temperature of 60° C. or higher is acceptable, and a temperature of 70° C. or higher and 80° C. or higher is preferable because it can be said that the heat resistance and strength are further improved.

Table 1 shows the composition and evaluation results.

10 stage 20 curable composition 30 electron beam/electromagnetic wave 40 cured product

Japanese Patent No. 5605589 Japanese Patent No. 5774825 JP-A-10-101754 Japanese Patent No. 3971412

Claims (7)

A curable liquid composition polymerized by at least one of an electron beam and an electromagnetic wave,
including a thermosetting resin precursor, a polymerization initiator, and fibers;
is liquid at 23°C,
The fibers have a fiber diameter of 2 to 25 μm, a fiber length of 50 μm or more and 300 μm or less , and are contained in a total of 20% or more and 60% or less by mass with respect to the curable liquid composition,
The thermosetting resin is an unsaturated polyester resin,
The curable liquid composition after curing has a deflection temperature under load of 120° C. or higher when a load of 1.8 MPa is applied according to the measurement method of JIS K7191.
The fiber diameter and fiber length of the fiber represent average values, and the curable liquid composition after curing is measured with a scanning electron microscope (SEM), and the average of five points is obtained. A curable liquid composition for stereolithography , which is obtained by : 2. The curable liquid composition according to claim 1, wherein the polymerization initiator is one or more selected from radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators and photothermal conversion agents. 3. The curable liquid composition according to claim 1, wherein the thermosetting resin precursor comprises a monomer, an oligomer, or a mixture of a monomer and an oligomer that is polymerized by electron beams or electromagnetic waves. 4. The curable liquid composition according to any one of claims 1 to 3, wherein said fiber is one or more selected from glass fiber and aramid fiber. A cured product comprising the curable liquid composition according to any one of claims 1 to 4 . a thin layer forming step of forming a thin layer of the curable liquid composition on or under the stage;
a curing step of irradiating at least part of the thin layer with at least one of an electron beam and an electromagnetic wave to cure the thin layer;
A method for producing a cured product, wherein the curable liquid composition is the curable liquid composition according to any one of claims 1 to 4 . a thin layer forming means for forming a thin layer of a curable liquid composition on or under the stage;
a curing means for curing by irradiating at least part of the thin layer with at least one of an electron beam and an electromagnetic wave;
An apparatus for producing a cured product, wherein the curable liquid composition is the curable liquid composition according to any one of claims 1 to 4 .

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