JP2019157088A - Cure-type composition, cured product, method for producing cured product, and apparatus for producing cured product - Google Patents

Abstract

To provide a cure-type composition that yields a cured product having a high strength per specific gravity.SOLUTION: Provided is a cure-type composition which is a cure-type composition cured by a light having a wavelength of 350 nm to 420 nm, and the cure-type composition contains a polymerizable compound and a filler, the filler contains a light-transmitting filler that transmits the light by 75% or more, and a light-blocking filler that blocks the light by 40% or more, and at least one of the fillers is an organic filler.SELECTED DRAWING: Figure 1A

Description

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

  A technique called additive manufacturing (AM) is known as a technique for modeling a three-dimensional three-dimensional object (three-dimensional object). This technique is a technique for manufacturing a three-dimensional structure by calculating a cross-sectional shape that is cut in the stacking direction of the three-dimensional structure, and forming and stacking a layered structure (modeling layer) according to the calculated cross-sectional shape.

  As an apparatus for manufacturing a three-dimensional structure, for example, an SLA (stereolithography) type modeling apparatus is known (for example, Patent Documents 1 and 2). This stereolithography type modeling apparatus forms a three-dimensional model formed of a cured product of the curable resin solution by curing and curing the curable resin solution layer by layer with an ultraviolet laser.

  As materials used for the curable resin solution in the stereolithography type modeling apparatus, for example, dimethyl acrylate, urethane acrylate, and the like are known (for example, Patent Document 3). It is also known to use a radiation curable composition containing a (meth) acrylate compound or a urethane (meth) acrylate compound in a stereolithography type modeling apparatus (for example, Patent Document 4).

Furthermore, a method for improving the strength of a three-dimensional structure made of a cured product of a curable resin solution by adding inorganic particles such as glass and ceramics to the curable resin solution in a stereolithography type modeling apparatus is known. (For example, Patent Documents 5 and 6).
However, in the above method, since inorganic particles having a large specific gravity are added, the specific gravity of the cured product of the curable resin solution may increase.

  An object of this invention is to provide the curable composition used as the hardened | cured material with high intensity | strength per specific gravity.

The curable composition of the present invention as a means for solving the problem is
A curable composition that is cured by light having a wavelength of 350 nm to 420 nm,
The curable composition includes a polymerizable compound and a filler,
The filler includes a light transmissive filler that transmits light by 75% or more and a light blocking filler that blocks light by 40% or more,
At least one of the fillers is an organic filler.

  According to this invention, the curable composition used as the hardened | cured material with high intensity | strength per specific gravity can be provided.

Drawing 1A is an explanatory view for explaining one embodiment of the manufacturing method of the hardened material of the present invention. Drawing 1B is an explanatory view for explaining one embodiment of a manufacturing method of hardened material of the present invention. Drawing 1C is an explanatory view for explaining one embodiment of a manufacturing method of hardened material of the present invention. FIG. 2A is an explanatory diagram for explaining another embodiment of the method for producing a cured product of the present invention. FIG. 2B is an explanatory diagram for explaining another embodiment of the method for producing a cured product of the present invention. FIG. 2C is an explanatory diagram for explaining another embodiment of the method for producing a cured product of the present invention.

(Curable composition)
The curable composition of the present invention is a curable composition that is cured by light having a wavelength of 350 nm to 420 nm, and the curable composition includes a polymerizable compound and a filler. The filler of the curable composition of the present invention includes the above-described light-transmitting filler that transmits 75% or more of the light and the above-described light-blocking filler that blocks 40% or more of the light. Here, at least one of the fillers of the curable composition of the present invention is an organic filler. The curable composition of the present invention further contains other components as necessary.

The present invention is based on the knowledge that a cured product of a curable composition of the prior art may have a low strength per specific gravity (specific strength).
Specifically, for example, when inorganic particles having a large specific gravity such as glass and ceramics are added to the curable composition as in the curable composition (curable resin solution) described in Patent Document 5 or 6. May increase the specific gravity of the curable composition. In this case, even if the strength of the cured product is improved by adding inorganic particles having a large specific gravity to the curable composition, the specific gravity of the cured product increases with the addition of the inorganic particles. It is difficult to improve the specific strength.

In recent years, in order to reduce the weight of parts to be manufactured, technology for designing parts with complex shapes that have been cut out from the results of simulations such as topology optimization that have been determined to be unnecessary is becoming popular. Yes. Since the stereolithography type modeling apparatus can easily model a cured product having a complicated shape, application to the production of a part designed by the above-described technique is being studied.
However, even when using stereolithography modeling equipment, if the strength of the cured product of the curable composition to be used is low or the specific gravity is large (specific strength is low), the weight of the parts to be manufactured is reduced while maintaining the strength. Difficult to do.

  Since the curable composition of the present invention becomes a cured product having a high strength per specific gravity, the conventional problems described above can be solved.

<Polymerizable compound>
The polymerizable compound means a compound that undergoes a polymerization reaction when energy is applied. In the present invention, the polymerizable compound is also a precursor of a curable resin described later.
The polymerizable compound is not particularly limited as long as it is polymerized to become a curable resin by applying energy, and can be appropriately selected according to the purpose. For example, a monomer, an oligomer, a mixture of a monomer and an oligomer, etc. Is mentioned.

  The monomer is not particularly limited as long as it is a polymerizable monomer, and can be appropriately selected according to the purpose. Examples thereof include monofunctional monomers and polyfunctional monomers, and include polymerizable oligomers and polymerizable polymers (macromonomers). Also good.

-Monofunctional monomer-
There is no restriction | limiting in particular as a monofunctional monomer, According to the objective, it can select suitably, For example, hydroxyethyl (meth) acrylamide, (meth) acryloyl morpholine, dimethylaminopropyl acrylamide, isobornyl (meth) acrylate, adamantyl ( (Meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 3,3,5-trimethyl Cyclohexane (meth) acrylate, t-butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl ( Acrylate), 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, phenoxyethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolane- 4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

-Multifunctional monomer-
There is no restriction | limiting in particular as a polyfunctional monomer, According to the objective, it can select suitably, For example, a bifunctional monomer, a trifunctional or more monomer, etc. are mentioned.

  There is no restriction | limiting in particular as a bifunctional monomer, According to the objective, it can select suitably, For example, neopentyl glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate , Propylene oxide (PO) adduct di (meth) acrylate of bisphenol A, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, bis Enol A ethylene oxide (EO) adduct di (meth) acrylate, bis (4- (meth) acryloxypolyethoxyphenyl) propane, diallyl phthalate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dimethylol tricyclodecanedi (Meth) acrylate, bisphenol A diglycidyl ether (meth) acrylic acid adduct, modified bisphenol A di (meth) acrylate and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the tri- or higher functional monomer include EO-modified pentaerythritol tri (meth) acrylate, PO-modified pentaerythritol tri (meth) acrylate, EO-modified pentaerythritol tetra (meth) acrylate, PO-modified pentaerythritol tetra (meth) acrylate, EO-modified dipentaerythritol tetra (meth) acrylate, PO-modified dipentaerythritol tetra (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-modified tetramethylolmethanetetra (Meth) acrylate, PO-modified tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate , Triallyl trimellitate, tetramethylolmethane tri (meth) acrylate, modified glycerin tri (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) Acrylate tolylene diisocyanate urethane prepolymer, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate Urethane prepolymer, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane prepolymer, urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate oligomer, polyether acrylate oligomer, silicone acrylate oligomer, etc. It is done. These may be used individually by 1 type and may use 2 or more types together.

The curable resin means a resin that cures when energy is applied.
There is no restriction | limiting in particular as curable resin, According to the objective, it can select suitably, For example, a photocurable resin, a thermosetting resin, etc. are mentioned.

  Examples of the photocurable resin include (meth) acrylate compounds and urethane (meth) acrylate compounds. Specific examples of the photocurable resin include phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3 -Methoxybutyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meta Acrylate, methoxydoxylethyl (meth) acrylate, ethyl diglycol (meth) acrylate, cyclic trimethylolpropane formal mono (meth) acrylate, imide (meth) acrylate, isoamyl (meth) acrylate, ethoxylated succinic acid (meth) acrylate , Trifluoroethyl (meth) acrylate, ω-carboxypolycaprolactone mono (meth) acrylate, N-vinylformamide, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methylphenoxyethyl (meth) acrylate, 4-t-butyl Cyclohexyl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, tribromophenyl (meth) acrylate, ethoxylated tribromoph Enenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, acryloylmorpholine, phenoxydiethylene glycol (meth) acrylate, vinylcaprolactam, vinylpyrrolidone, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1,4-cyclohexanedi Methanol mono (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, stearyl (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 3, 3 , 5-trimethylcyclohexanol (meth) acrylate, isooctyl (meth) acrylate, octyl / decyl (meth) acrylate, tridecyl (meth) Acrylate, caprolactone (meth) acrylate, ethoxylated (4) nonylphenol (meth) acrylate, methoxypolyethylene glycol (350) mono (meth) acrylate, methoxypolyethylene glycol (550) mono (meth) acrylate, hexadiol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, bispentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethoxylated 1,6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl 1,3-propanediol di (meth) acrylate, neopentyl glycol hydroxypivalate Di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, hydroxypivalate trimethylolpropane tri (meth) acrylate, ethoxylated tri (meth) acrylate , Ethoxylated tripropylene glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylolpropane tri ( (Meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, propoxylate glyceryl tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pet Taerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, neopentyl glycol oligo (meth) acrylate, 1,4 -Butanediol oligo (meth) acrylate, hydroxypivalate neopentyl glycol acrylic acid adduct, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, ethoxy Neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol Ruji (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and acrylic acid 2- (2-vinyloxy ethoxy) ethyl. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the thermosetting resin include phenol resin, unsaturated polyester resin, polyimide resin, epoxy resin, urethane resin, alkyd resin, diallyl phthalate resin, and the like. These may be used individually by 1 type and may use 2 or more types together.

<Filler>
A filler means the substance with which a curable composition is filled.
The curable composition of the present invention includes a light-transmitting filler that transmits 75% or more of light having a wavelength of 350 nm to 420 nm, and a light-blocking filler that blocks 40% or more of the light described above. Here, at least one of the fillers of the curable composition of the present invention is an organic filler.

<< light transmissive filler >>
The light-transmitting filler means a filler that transmits 75% or more of light having a wavelength of 350 nm to 420 nm. Hereinafter, the ratio (%) at which the filler transmits light may be referred to as transmittance.
There is no restriction | limiting in particular as a light transmissive filler, According to the objective, it can select suitably, For example, Glasses, such as glass bead and glass fiber, Polyolefin, such as polyethylene and a polypropylene, Polycarbonate, Polyester etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

<< light blocking filler >>
The light blocking filler means a filler that blocks 40% or more of light having a wavelength of 350 nm to 420 nm.
Here, the ratio (%) at which the light blocking filler blocks light is a value obtained by subtracting the transmittance of the light blocking filler from 100% (for example, the transmittance of the light blocking filler is 20%). , The ratio of the light blocking filler to block light is 80%).
The light blocking filler is not particularly limited and can be appropriately selected according to the purpose. For example, carbon fiber such as carbon fiber, carbon nanofiber, graphite, graphene, aramid fiber, zylon fiber, organically modified viscosity mineral, organic Examples thereof include a pigment composition. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, the transmittance | permeability of a light-transmitting filler and a light-blocking filler can be measured by conducting a test according to JIS R3106 using an ultraviolet-visible near-infrared spectrophotometer manufactured by Shimadzu Corporation. .

<<< Organic filler >>>
An organic filler means the filler formed with organic substance.
The organic filler is not particularly limited and can be appropriately selected depending on the purpose. For example, polyolefin such as polyethylene and polypropylene, polycarbonate, polyester, polyvinyl alcohol, aramid fiber, polyethylene fiber, xylon fiber, boron fiber, pulp, cellulose Examples thereof include nanofibers, organic modified viscosity minerals, and organic pigment compositions. These may be used individually by 1 type and may use 2 or more types together.

In addition, as long as at least one of the fillers described above is an organic filler, the other filler may be an inorganic filler.
An inorganic filler means the filler formed with the inorganic substance.
There is no restriction | limiting in particular as an inorganic filler, According to the objective, it can select suitably, For example, glass beads, such as glass bead and glass fiber, or carbon fiber, such as carbon fiber, carbon nanofiber, graphite, and graphene, or silica filler And ceramic fillers such as alumina filler and zirconia filler, or lightweight metal fibers such as aluminum and magnesium. These may be used individually by 1 type and may use 2 or more types together.

Moreover, there is no restriction | limiting in particular as a shape of the filler mentioned above, According to the objective, it can select suitably, For example, spherical shape, needle shape, fiber shape, flat scale shape etc. are mentioned. As the width and length of the filler, the width is preferably 0.1 μm or more and 50 μm or less, the length is preferably 10 μm or more, more preferably 10 μm or more and 30 μm or less, and the length is more preferably 50 μm or more.
Here, the width and length of the filler mean the respective average values, and can be obtained from the results of measurement by a scanning electron microscope (SEM) for the filler contained in the cured product. . Specifically, using a scanning electron microscope, from among a large number of fillers contained in the cured product, five fillers are arbitrarily selected to measure the width and length, and the measured width and The average length can be taken as the width and length of the filler.

There is no restriction | limiting in particular as content of the filler with respect to the total amount of a curable composition except the case where it is not contained at all, It can select suitably according to the objective. The filler is preferably contained in an amount of 2% by volume or more with respect to the total amount of the curable composition, for example. When the curable composition contains 2% by volume or more of the filler, the specific strength of the cured product obtained by curing the curable composition is improved.
Moreover, it is preferable that a filler is contained 90 volume% or less with respect to the total amount of a curable composition, for example. When the curable composition contains 90% by volume or less of the filler, the curable composition can be easily cured to form a cured product from the balance of the amount with the polymerizable compound.

  Further, the filler is preferably contained in an amount of 10% by volume or more and 50% by volume or less, preferably 20% by volume or more and 40% by volume or less, in consideration of the viscosity of the curable composition with respect to the total amount of the curable composition. It is more preferable. In particular, when the curable composition contains 20% by volume or more and 40% by volume or less of the filler, the specific strength of the cured product of the curable composition can be further improved.

  The content of the light transmissive filler relative to the total amount of the filler is not particularly limited unless it is not included at all, and can be appropriately selected according to the purpose. The light transmissive filler is preferably, for example, 50% by volume or more with respect to the total amount of the filler. When the filler contains 50% by volume or more of the light transmissive filler, since the curable composition is cured without unevenness when cured, the specific strength of the cured product can be further improved.

  Further, the content of the organic filler relative to the total amount of the filler is not particularly limited unless it is not included at all, and can be appropriately selected according to the purpose. The organic filler is preferably, for example, 50% by volume or more with respect to the total amount of the filler. When the filler contains 50% by volume or more of the organic filler, a large amount of organic filler having a small specific gravity is contained. Therefore, the specific gravity of the cured product of the curable composition is also reduced, so that the specific strength of the cured product can be reduced. It can be improved further.

  From the viewpoint of improving the adhesion between the filler and the polymerizable compound, it is preferable to perform a surface treatment of the filler. Examples of the surface treatment of the filler include a hydrophobic treatment.

  The method of hydrophobizing treatment is not particularly limited as long as the surface of the filler is hydrophobized, and can be appropriately selected according to the purpose. Examples of the hydrophobizing agent used in the hydrophobizing treatment include silane coupling agents such as hexamethyldisilazane and dimethyldichlorosilane, and silicone oil treating agents such as dimethyl silicone oil and amino-modified silicone oil. A coupling agent is preferred.

<Light>
The light is not particularly limited as long as it has a wavelength in the range of 350 nm to 420 nm. For example, it refers to an electromagnetic wave in the ultraviolet light region to the visible light region. The light may be light directly emitted from a light irradiation means described later, or may be light extracted through an optical filter.

There is no restriction | limiting in particular as a means to irradiate light, According to the objective, it can select suitably. As a means for irradiating light, for example, a fluorescent lamp, a metal halide lamp, a mercury lamp, a xenon lamp, a discharge tube such as a neon tube, an incandescent bulb, an LED (Light Emitting Diode), a semiconductor laser irradiator (Laser Diode), an organic EL (Electro-Luminescence), inorganic EL, ultraviolet (UV) irradiator, DLP (Digital Light Processing, registered trademark) light source, and the like.
There may be two or more types of light applied to the curable composition, and they may be used simultaneously or sequentially.
In the case where the polymerization initiator described later is contained in the curable composition, it is preferable that the composition has sufficient strength to excite the polymerization initiator.

<Other ingredients>
Other components are not particularly limited and may be appropriately selected depending on the purpose. For example, polymerization initiator, antifoaming agent, sizing agent, crosslinking agent, viscosity reducing agent, surface treatment agent, plasticizer, smoothing agent, A solvent etc. are mentioned. Among these, it is preferable that a curable composition contains a polymerization initiator.

<< Polymerization initiator >>
The polymerization initiator means a substance that starts the polymerization reaction of the above-described polymerizable compound by absorbing light.
The polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, and photothermal conversion agents, and radical polymerization initiators are preferred. . These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as content of the polymerization initiator with respect to the whole curable composition, It can select according to the objective, for example, it is preferable that they are 0.01 mass% or more and 5 mass% or less.

  The radical polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, Thiophenyl group-containing compounds), hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

  There is no restriction | limiting in particular as a cationic polymerization initiator, According to the objective, it can select suitably, For example, aryl sulfonium salt and aryl iodonium salt which are onium salts, N-vinyl carbazole, a thioxanthone compound, 9,10-di And anthracene compounds such as butoxyanthracene.

  The anionic polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include o-nitrobenzyl carbamate, α, α-dimethylbenzyl carbamate, α-keto carbamate derivative, N-hydroxyimido carbamate, and the like. Primary amine or secondary amine, ammonium of phenylglyoxylate, benzhydryl ammonium salt, N-benzophenone methyl-tri-N-alkyl ammonium borate, quaternary α-ammonium acetophenone salt Examples thereof include salts of acid salts, dithiocarbamates, thiocyanates, and other counter ions, or amine imide derivatives.

  The photothermal conversion agent is not particularly limited and can be appropriately selected depending on the purpose. For example, a casocyanine compound, a polymethine compound, an aminium compound, a diimonium compound, a phthalocyanine compound, a merocyanine compound, a benzenethiol metal complex , Mercaptophenol metal complexes, aromatic diamine metal complexes, nickel complex compounds, anthraquinone compounds, naphthalocyanine compounds, indolenine compounds, and the like.

  The curable composition of the present invention can be suitably used for forming articles such as electronic device parts, automobile part prototypes, and small lot products such as automobile dress-up tools. Since the cured product of the curable composition of the present invention has high specific strength, it can withstand use as a practical product.

(Cured product)
The cured product (also referred to as a modeled product) of the present invention comprises the curable composition of the present invention, and can be obtained by irradiating at least one of light to the curable composition and curing it.
The cured product of the present invention is not particularly limited as long as the curable composition of the present invention is cured. The cured product of the present invention is limited to a product produced by the method for producing a cured product of the present invention described later or a production device for a cured product. For example, it may be manufactured by an ink jet type modeling apparatus or the like.

  The cured product of the present invention preferably has a specific bending strength of 30 MPa or more. When the specific bending strength is 30 MPa or more, the cured product can be suitably used for components that require strength. In addition, specific bending strength of hardened | cured material can be calculated | required by performing the test according to JISK7171 using a precision universal testing machine (autograph).

(Method for producing cured product, production device for cured product)
The manufacturing method of the hardened | cured material of this invention includes the supply process which supplies a curable composition on a stage or under a stage. Furthermore, the manufacturing method of the hardened | cured material of this invention includes the hardening process hardened | cured by irradiating the light whose wavelength is 350 nm-420 nm at least one part of the supplied curable composition. Moreover, as for the manufacturing method of the hardened | cured material of this invention, a curable composition is the curable composition of this invention, and includes another process as needed.
The apparatus for producing a cured product of the present invention has a supply means for supplying a curable composition on or under a stage. Furthermore, the manufacturing apparatus of the hardened | cured material of this invention contains the hardening means to harden | cure at least one part of the supplied curable composition by irradiating the light whose wavelength is 350 nm-420 nm. Moreover, as for the manufacturing apparatus of the hardened | cured material of this invention, a curable composition is a curable composition of this invention, and has another means as needed.
The method for producing a cured product can be suitably performed by a production device for a cured product, the supplying step can be suitably performed by a supplying unit, the curing step can be suitably performed by a curing unit, and the other steps are This can be done by other means.

  That is, since the manufacturing apparatus of the hardened | cured material of this invention is synonymous with implementing the manufacturing method of the hardened | cured material of this invention, it mainly manufactures the hardened | cured material of this invention through description of the manufacturing apparatus of the hardened | cured material of this invention. The details of the method are also clarified.

<Supply means, supply process>
The supply means supplies the curable composition on or under the stage.
In the supplying step, the curable composition is supplied on the stage or below the stage by the supplying means.

  The supply means is not particularly limited and can be appropriately selected according to the purpose. For example, the stage where a cured product (modeled product) is modeled, which is adopted in a stereolithography type modeling apparatus of the free liquid surface method, is lowered. The mechanism which supplies a curable composition by doing is mentioned. Moreover, as a supply means, the mechanism which supplies the curable composition by raising the stage by which the modeling object is modeled, for example employ | adopted with the stereolithography type modeling apparatus of a control liquid level method may be sufficient.

A stereolithography type modeling apparatus using a free liquid level method supplies a curable composition onto a stage by lowering a stage disposed in a tank to which the curable composition is supplied by a predetermined distance. The supplied curable composition is cured by a curing means described later to form a thin layer made of a cured product.
Also, depending on the viscosity of the curable composition, the surface of the supplied curable composition may be difficult to be flat, so that the supply means may planarize the surface of the curable composition as necessary. You may have.

  The stereolithography type modeling apparatus of the regulated liquid level method supplies the curable composition under the stage by raising the stage disposed in the tank to which the curable composition is supplied by a predetermined distance. The supplied curable composition is cured by a curing means described later to form a thin layer made of a cured product.

<Curing means, curing process>
The curing means cures at least a part of the supplied curable composition by irradiating light having a wavelength of 350 nm to 420 nm.
In the curing step, at least a part of the supplied curable composition is cured by irradiating light having a wavelength of 350 nm to 420 nm by a curing means.

  The curing means is not particularly limited as long as it can irradiate light that can be cured by applying energy to the curable composition, and can be appropriately selected according to the purpose. Examples of the curing means include fluorescent lamps, metal halide lamps, mercury lamps, xenon lamps, neon lamps and other discharge tubes, incandescent bulbs, LEDs (Light Emitting Diodes), semiconductor laser irradiators (Laser Diodes), organic EL (Electro- Luminescence), inorganic EL, ultraviolet (UV) irradiator, DLP (Digital Light Processing, registered trademark) light source, and the like.

  When irradiating light, the curing unit may irradiate the light to a desired position while moving to a desired position, or may irradiate a certain range at once. The range of irradiation can be changed as appropriate. The narrower the range of irradiation, the more precise the cured product can be obtained. As a direction in which the curing means irradiates light, the stage may be irradiated from above or from below.

  In addition, there is no restriction | limiting in particular as a method of irradiating light to a desired location and hardening a curable composition, According to the objective, it can select. For example, a method of changing an irradiation position using an fθ lens and a galvano mirror, a method of changing an irradiation position using an fθ lens and a polygon mirror, a method of moving a curing unit to a desired position, and a stage with respect to the curing unit The method of moving relatively is mentioned.

  The light irradiated by the curing means is not particularly limited as long as it has a wavelength in the range of 350 nm to 420 nm, and refers to, for example, an electromagnetic wave in the ultraviolet light region or visible light region. The light irradiated by the curing unit may be light directly irradiated by the curing unit, or may be light extracted through an optical filter.

  The apparatus for producing a cured product of the present invention repeats a supply step of supplying a curable composition by a supply unit and a curing step of curing the curable composition by a curing unit by a predetermined number of times, so that the curable composition is obtained. A thin layer made of the cured product is laminated to produce a shaped product.

<Other means, other processes>
There is no restriction | limiting in particular as another means, According to the objective, it can select suitably, For example, a heating means, a stirring means, etc. are mentioned.
There is no restriction | limiting in particular as another process, According to the objective, it can select suitably, For example, a heating process, a stirring process, etc. are mentioned.
The heating step can be preferably performed by a heating unit, the stirring step can be preferably performed by a stirring unit, and the flattening step can be preferably performed by a flattening unit.

The heating means is not particularly limited as long as the cured product of the curable composition can be heated, and can be appropriately selected according to the purpose. Examples thereof include an infrared (IR) heater.
By heating the cured product of the curable composition at a timing during the production of the modeled object and at least after the modeled object is manufactured by the heating means, the heat resistance and specific strength of the cured product can be further improved. it can.

The stirring means is not particularly limited as long as the curable composition can be stirred, and can be appropriately selected according to the purpose. For example, the stirring is performed by rotating a blade-shaped component and stirring by ultrasonic vibration. Mechanism and the like.
There is no restriction | limiting in particular as timing which a stirring means stirs a curable composition, According to the objective, it can select suitably, For example, before a supply means supplies a curable composition etc. are mentioned.
By stirring the curable composition with the stirring means, the viscosity of the curable composition temporarily decreases, so that even a highly viscous curable composition can be easily manufactured, and the curable mold can be manufactured. Unevenness of each component in the composition can be prevented, and a highly precise cured product can be easily obtained.

  The cured product production apparatus of the present invention is preferably a cured product production apparatus of the above-described regulated liquid level method because the production of the cured product is easy even if it is a curable composition having a high viscosity. Moreover, as a manufacturing apparatus of the hardened | cured material of a control liquid level method, the hardened | cured material of the two-dimensional control system described in the one-dimensional control system hardened | cured material described in patent 5774825, for example, patent 5605589 A manufacturing apparatus or the like can be used.

  Hereinafter, although one embodiment is described about the manufacturing method of the hardened material of the present invention, the present invention is not limited to the following embodiment.

Drawing 1A-Drawing 1C are explanatory views for explaining one embodiment of the manufacturing method of the hardened material of the present invention.
First, as shown in FIG. 1A, the thin layer 20 is formed on the stage 10 by supplying the curable composition in the supplying step.
Next, as shown in FIG. 1B, in the curing step, at least a part of the thin layer 20 is irradiated with light 30 from the upper side with respect to the stage 10 to be cured.
And as shown to FIG. 1C, the hardened | cured material 40 is modeled by hardening at least one part of the thin layer 20. As shown in FIG. Next, in the supplying step, the stage 10 is lowered in the direction of the arrow in FIG. 1C to supply the curable composition to form a thin layer that becomes the next layer.
Thus, in one embodiment of the method for producing a cured product of the present invention, by repeating the supplying step and the curing step, the cured product 40 is laminated on the stage 10 to form a modeled object (three-dimensional modeled object). To manufacture.

2A to 2C are explanatory diagrams for explaining another embodiment of the method for producing a cured product of the present invention.
First, as shown in FIG. 2A, a thin layer 20 is formed under the stage 10 by supplying the curable composition in the supplying step.
Next, as shown in FIG. 2B, in the curing process, at least a part of the thin layer 20 is irradiated with light 30 from the lower side of the stage 10 to be cured.
And as shown to FIG. 2C, the hardened | cured material 40 is modeled by hardening at least one part of the thin layer 20. As shown in FIG. Next, in the supplying step, the stage 10 is raised in the direction of the arrow in FIG. 2C to supply the curable composition to form a thin layer that becomes the next layer.
As described above, in another embodiment of the method for producing a cured product of the present invention, the cured product 40 is laminated under the stage 10 by repeating the supplying process and the curing process, thereby forming a modeled object (three-dimensional modeled object). ).

  Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the following examples.

Example 1
<Preparation of base resin liquid 1>
First, 18 parts by mass of tricyclodecane dimethanol diacrylate (trade name: NK-A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: A9550W) 2 parts by mass, manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of polyethylene glycol monoacrylate (trade name: Blemmer AE200, manufactured by Nippon Oil & Fats Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (trade name: HBE100, Shin Nippon Rika) 50 parts by mass), 5 parts by mass of bisphenol A diglycidyl ether (trade name: EP-4100E, manufactured by ADEKA)
10 parts by mass of 3-ethyl-3-hydroxymethyloxetane (trade name: OXT-101, manufactured by Toagosei Co., Ltd.) was mixed to obtain a mixed solution 1.

  In a light-shielded room, 4 parts by mass of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Irgacure 1173, manufactured by BASF) is mixed with the liquid mixture 1 to obtain a matrix resin liquid 1 Was made.

<Production of Filler 1>
Polyethylene fiber (trade name: Dyneema SK60, manufactured by Toyobo Co., Ltd., hereinafter referred to as “PE1”) and 25% by volume are added to the sealed container, followed by glass fiber (trade name: SS05-404, Nittobo). 25 vol% was added. Further, 50% by volume of carbon fiber (trade name: M-2007S, manufactured by Kureka Co., Ltd., hereinafter referred to as “CF1”) was added, and the mixture was stirred by hand to obtain a filler 1.

<Preparation of curable composition 1>
Add 75% by volume of base resin liquid 1 and 25% by volume of filler 1 with respect to the entire curable composition, and stir for 5 minutes with planetary stirring and defoaming device Mazerustar KK-400W (Kurabo). A curable composition 1 was obtained.

<Preparation of cured product 1>
200 mL of the curable composition 1 obtained above was weighed, using a DWS 028J, the lamination pitch was 50 μm, the laser speed was the set value 275 for the first and second layers, the set value 4400 for the third and subsequent layers. The cured product 1 was produced by setting to 1. In this example, the curable composition 1 was irradiated with laser light having a wavelength of 405 nm using a semiconductor laser irradiator using 028J manufactured by DWS.
The obtained cured product 1 was thoroughly dried with ethanol and then naturally dried. As the cured product 1, three bending test pieces described in JIS K7171 were prepared so that the Z-axis direction was the longest side.

In addition, in the following Examples 2-25 and Comparative Examples 1-12, the set value after the third layer of the laser speed is selected from 4400, 2200, and 275 according to the curability of the cured product 2 to 37, The maximum value that can cure the cured product was used. When the set value after the third layer of the laser speed is a large value, the time required for manufacturing the cured product (modeling time) can be shortened, and the productivity of the cured product can be increased.
In Examples 1-25 and Comparative Examples 1-12, the thickness (thickness per layer) of the cured product is set to 0.050 mm, and a shaped product having an overall thickness of 4 layers consisting of 80 thin layers is obtained. Produced. In this case, when the setting value of the third and subsequent layers of the laser speed is 4400, the time required to form one thin layer is about 30 seconds to 60 seconds. Including the time required, the time required to produce the entire cured product was about 40-80 minutes. When the setting value of the third and subsequent layers of the laser speed is 2200, the time required to form a thin layer one layer is about 60 seconds to 90 seconds, which is required for other behavior of the manufacturing apparatus. The time required for the production of the entire cured product was about 80 minutes to 120 minutes. In addition, when the setting value of the third and subsequent layers of the laser speed is 275, the time required to form one thin layer is about 480 seconds to 510 seconds, which is necessary for other behavior of the manufacturing apparatus. The time required for manufacturing the entire cured product was about 640 minutes to 680 minutes.

(Example 2)
In Example 2, instead of the filler 1, 50 volume% of polyethylene fiber (trade name: Dyneema SK60, manufactured by Toyobo Co., Ltd., hereinafter referred to as “PE1”) was added to the sealed container as a filler. Further, 50% by volume of CF1 was added, and a cured product 2 was produced in the same manner as in Example 1 except that the filler 2 produced by shaking with shaking was used.

(Example 3)
In Example 3, in place of the filler 1, polypropylene pellets (trade name: experimental resin pellets polypropylene, manufactured by Sun Platec Co., Ltd.) were freeze pulverized to produce polypropylene powder (hereinafter referred to as “PP1”). Then, 50% by volume of PP1 is added as a filler to the sealed container, 50% by volume of CF1 is further added, and the filler 3 prepared by hand shaking is used in the same manner as in Example 1 to obtain the cured product 3. Produced.

Example 4
In Example 4, instead of the filler 1, polycarbonate pellets (trade name: experimental resin pellets polycarbonate, manufactured by Sampratec) were freeze-pulverized to produce polycarbonate powder (hereinafter referred to as “PC1”). Then, 50% by volume of PC1 is added as a filler to the sealed container, 50% by volume of CF1 is further added, and the cured product 4 is prepared in the same manner as in Example 1 except that the filler 4 prepared by shaking with shaking is used. Produced.

(Example 5)
In Example 5, instead of the filler 1, 50% by volume of polyester fiber cut fiber (trade name: Tetron, manufactured by Toray Industries, Inc., hereinafter referred to as “PES1”) was added to the sealed container as a filler. Further, a cured product 5 was produced in the same manner as in Example 1 except that 50% by volume of CF1 was added and the filler 5 produced by shaking with shaking was used.

(Example 6)
In Example 6, instead of the filler 1, 50% by volume of acrylic fiber cut fiber (trade name: Torelon, manufactured by Toray Industries, Inc., hereinafter referred to as “PAN1”) was added to the sealed container as a filler. Further, a cured product 6 was produced in the same manner as in Example 1 except that 50% by volume of CF1 was added, and the filler 6 produced by shaking with shaking was used.

(Example 7)
In Example 7, instead of the filler 1, 50% by volume of cellulose nanofiber (trade name: Serenpia, manufactured by Nippon Paper Industries Co., Ltd., hereinafter referred to as “CNF1”) was added to the sealed container as a filler. Further, a cured product 7 was produced in the same manner as in Example 1 except that 50% by volume of CF1 was added and the filler 7 prepared by shaking and shaking was used.

(Example 8)
In Example 8, instead of the curable composition 1, the base resin liquid 1 was added to 98% by volume and the filler 2 was added by 2% by volume, and the planetary stirring and defoaming device Mazerustar KK-400W (manufactured by Kurabo Industries) was used. A cured product 8 was produced in the same manner as in Example 2 except that the curable composition 2 produced by stirring for 5 minutes was used.

Example 9
In Example 9, instead of the curable composition 1, 50% by volume of the base resin liquid 1 and 50% by volume of the filler 2 were added, and the planetary stirring and defoaming device Mazerustar KK-400W (manufactured by Kurabo Industries Co., Ltd.) A cured product 9 was produced in the same manner as in Example 1 except that the curable composition 3 produced by stirring for 5 minutes was used.

(Example 10)
In Example 10, instead of the curable composition 1, 10% by volume of the base resin liquid 1 and 90% by volume of the filler 2 were added, and the planetary stirring and defoaming device Mazerustar KK-400W (manufactured by Kurabo Industries Co., Ltd.) A cured product 10 was prepared in the same manner except that the curable composition 4 prepared by stirring for 5 minutes was used.

(Example 11)
In Example 11, instead of the base resin liquid 1, an unsaturated polyester resin (trade name: LP-921-N, manufactured by DIC) 99% by mass and radical polymerization initiator 1 (trade name: irgacure 1173, manufactured by BASF) Was mixed to prepare a base resin liquid 2. Then, in place of the filler 1, 50% by volume of PE1 was added to the sealed container, 25% by volume of GF1 was added, 25% by volume of CF1 was added, and the filler 8 obtained by hand shaking was used. A cured product 11 was produced in the same manner as in Example 1.

(Example 12)
In Example 12, a cured product 12 was produced in the same manner as in Example 2 except that the base resin liquid 2 was used instead of the base resin liquid 1.

(Example 13)
In Example 13, instead of the filler 2, 25% by volume of PE1 and 50% by volume of GF1 were added to the sealed container, and an aramid fiber cut fiber (trade name: Twaron, manufactured by Teijin Ltd., hereinafter “Aramid 1”). The cured product 13 was produced in the same manner as in Example 2 except that the filler 9 obtained by shaking and shaking was used.

(Example 14)
In Example 14, instead of using aramid 1, a filler 10 prepared by adding 25% by volume of xylon fiber cut fiber (trade name: SYRON, manufactured by Toyobo Co., Ltd., hereinafter referred to as “Zylon 1”) is used. A cured product 14 was produced in the same manner as in Example 13.

(Example 15)
In Example 15, instead of aramid 1, a filler 11 produced by adding 25% by volume of pulp fiber (trade name: NP fiber W-10MG2, manufactured by Nippon Paper Industries Co., Ltd., hereinafter referred to as “pulp 1”) is used. Except for this, a cured product 15 was produced in the same manner as in Example 13.

(Example 16)
In Example 16, in place of CF1, a filler 12 produced by adding 25% by volume of carbon nanotubes (trade name: NC-1100, manufactured by Sigma-Aldrich, hereinafter referred to as “CNT1”) was used. A cured product 16 was produced in the same manner as in Example 11.

(Example 17)
In Example 17, Example 1 was used except that instead of CF1, a filler 13 produced by adding 25% by volume of aluminum fiber (trade name: KC Metal Fiber, manufactured by Niji Co., Ltd., hereinafter referred to as “AlF1”) was used. In the same manner as in No. 11, a cured product 17 was produced.

(Example 18)
In Example 18, it was carried out except that instead of CF1, a filler 14 produced by adding 25% by volume of talc (trade name: MS-T, manufactured by Nippon Talc Co., Ltd., hereinafter referred to as “talc 1”) was used. A cured product 18 was produced in the same manner as in Example 11.

(Example 19)
In Example 19, instead of the base resin liquid 1, 99% by mass of unsaturated polyester resin (trade name: LP-921-N, manufactured by DIC), photothermal conversion agent 1 (trade name: IR-806, Sigma-Aldrich) A cured product 19 was produced in the same manner as in Example 2 except that the base resin liquid 3 produced by mixing 1% by mass of the same material was used.

(Example 20)
In Example 20, instead of the base resin solution 1, 99% by mass of polyamic acid (trade name: Iupia AT, manufactured by Ube), which is a polyimide precursor, was added to an anionic initiator 1 (trade name: 2- (9- Oxanthanthen-2-yl) propionic Acid 1,5,7-Triazabicclo [4.4.0] dec-5-ene Salt, manufactured by TCI) 0.5 mass%, photothermal conversion agent 1 0.5 mass% mixed A cured product 20 was produced in the same manner as in Example 2 except that the base resin liquid 4 thus produced was used.

(Example 21)
In Example 21, instead of the base resin liquid 1, 49% by mass of liquid epoxy resin 1 (trade name: EPICLON EXA-4850, manufactured by DIC) and liquid epoxy resin 2 (trade name: EPICLON HP-4710, manufactured by DIC) ) 50% by mass, 0.5% by mass of the anionic initiator 1 and 0.5% by mass of the photothermal conversion agent 1 were used except that the base resin liquid 5 was used. Article 21 was produced.

(Example 22)
In Example 22, instead of the anionic initiator 1, a base resin liquid 6 prepared by mixing 0.5% by mass of a cationic initiator 1 (trade name: Adeka Arcles SP-170, manufactured by ADEKA) is used. Except for the above, a cured product 22 was produced in the same manner as in Example 21.

(Example 23)
In Example 23, instead of the base resin liquid 1, 50% by mass of phenol resin (trade name: EPICLON EXA-4850, manufactured by DIC), 49% by mass of liquid epoxy resin 2, and 0.3% of cationic initiator 1 A cured product 23 is prepared in the same manner as in Example 2 except that the base resin liquid 7 prepared by mixing 0.4% by mass of the mass%, the anion initiator 0.3%, and the photothermal conversion agent 1 is used. did.

(Example 24)
In Example 24, a cured product 24 was obtained in the same manner as in Example 12 except that the base resin liquid 8 produced using 99% by mass of diallyl phthalate resin (Sumitomo Bakelite Co., Ltd.) was used instead of the unsaturated polyester. Was made.

(Example 25)
In Example 25, in place of unsaturated polyester, urethane acrylate resin (trade name: CBZ500LM-AS, manufactured by Nippon Iupika Co., Ltd.) 49.5% by mass and urethane resin (trade name: Takenate 500, manufactured by Mitsui Chemicals) 49. 5% by mass was mixed. Further, a cured product was obtained in the same manner as in Example 12 except that the base resin liquid 9 prepared by mixing 0.5% by mass of the radical polymerization initiator 1 and 0.5% by mass of the photothermal conversion material 1 was used. 25 was produced.

(Comparative Example 1)
In Comparative Example 1, a cured product 26 was produced in the same manner as in Example 1 except that the base resin liquid 1 was used as it was as a curable composition.

(Comparative Example 2)
In Comparative Example 2, a cured product 27 was produced in the same manner as in Example 1 except that 25% by volume of GF1 was added to 75% by volume of the base resin liquid 1.

(Comparative Example 3)
In Comparative Example 3, production of the cured product 28 was attempted in the same manner as in Example 1 except that 25% by volume of CF1 was added to 75% by volume of the base resin liquid 1, but the curing was insufficient. Could not be produced.

(Comparative Example 4)
In Comparative Example 4, a cured product 29 was produced in the same manner as in Example 2 except that 50% by volume of GF1 was added instead of PE1.

(Comparative Example 5)
In Comparative Example 5, production of the cured product 30 was attempted in the same manner as Comparative Example 4 except that GF1 was 30% by volume and CF1 was 70% by volume. However, the cured product was insufficient and could not be produced.

(Comparative Example 6)
In Comparative Example 6, a cured product 31 was produced in the same manner as Comparative Example 2 except that the base resin liquid 2 was used instead of the base resin liquid 1.

(Comparative Example 7)
In Comparative Example 7, a cured product 32 was produced in the same manner as Comparative Example 4 except that the base resin liquid 2 was used instead of the base resin liquid 1.

(Comparative Example 8)
In Comparative Example 8, a cured product 33 was produced in the same manner as in Example 1 except that 25% by volume of PE1 was added as a filler to 75% by volume of the base resin liquid 1.

(Comparative Example 9)
In Comparative Example 9, a cured product 34 was prepared in the same manner as in Example 1 except that 25% by volume of PP1 was added as a filler to 75% by volume of the base resin liquid 1.

(Comparative Example 10)
In Comparative Example 10, a cured product 35 was produced in the same manner as in Example 1 except that 25% by volume of PC1 was added as a filler to 75% by volume of the base resin liquid 1.

(Comparative Example 11)
In Comparative Example 11, a cured product 36 was produced in the same manner as in Example 1 except that 25% by volume of PES1 was added as a filler to 75% by volume of the base resin liquid 1.

(Comparative Example 12)
In Comparative Example 12, a cured product 37 was produced in the same manner as in Example 1 except that 25% by volume of PAN1 was added as a filler to 75% by volume of the base resin liquid 1.

  The compositions of Examples 1 to 25 and Comparative Examples 1 to 12 described above are shown in Tables 1 to 7 below.

Here, the transmittance | permeability of the filler in Table 1-Table 7 can be measured by performing the test according to JIS R3106 using the Shimadzu Corporation ultraviolet visible near-infrared spectrophotometer. . Specifically, 10% filler and 84.9% water as a binder, 5% polyvinyl alcohol resin (trade name: JF-05, manufactured by NIPPON POVAR CO., LTD.), Leveling agent and dispersion aid as fluorine-based interface An activator (trade name: Megafax F477, manufactured by DIC) 0.1% was added and mixed. Next, the mixture was pulverized for 5 hours using φ0.5 mm zirconia beads, then mixed and pulverized for 5 hours using φ0.1 mm zirconia beads, and then applied onto a glass substrate using a spin coater. A coating film having a thickness of 1.0 μm to 5.0 μm was obtained. By measuring the light absorption spectrum and transmission spectrum of the obtained coating film using an ultraviolet visible near infrared (UV-Vis-NIR) spectrophotometer (trade name: UV-3600, manufactured by Shimadzu Corporation) The transmittance of the filler was measured.
Moreover, in Table 1-Table 7, the transmittance | permeability was shown about the light shielding filler. The proportion of the light blocking filler that blocks light can be determined by subtracting the transmittance of the light blocking filler from 100%.

(Evaluation)
Evaluation with respect to Examples 1 to 25 and Comparative Examples 1 to 12 is performed by measuring the time required for modeling the cured product (modeling time), the specific gravity and bending strength of the cured product, and calculating the specific bending strength. went.

<Laser speed>
With respect to Examples 1 to 25 and Comparative Examples 1 to 12, the upper limit of the set values of the third and subsequent layers of the laser speed that can produce a cured product was evaluated based on the following evaluation criteria for laser speed.
[Evaluation criteria for laser speed]
◎: The cured product could be produced by setting the laser speed setting value to 4400. ○: The cured product could not be produced when the laser speed setting value was 4400. What could be produced: A cured product could not be produced when the setting value of the laser speed was 4400 and 2200, but a cured product could be produced when the setting value was set to 275. X: The setting value of the laser speed was set to 275. However, the cured product could not be produced (it did not cure)

<Specific gravity>
Among Examples 1 to 25 and Comparative Examples 1 to 12, specific gravity was measured using a specific gravity measurement kit AD-1653 manufactured by A & D Co., for which a cured product could be produced.

<Bending strength>
Among Examples 1 to 25 and Comparative Examples 1 to 12, a cured product can be produced, a bending strength test is performed according to JIS K7171, using an autograph AG-X manufactured by Shimadzu Corporation. The bending strength was measured.

<Specific bending strength>
Of Examples 1 to 25 and Comparative Examples 1 to 12, the cured product can be produced, the specific bending strength is calculated by dividing the measured bending strength by the measured specific gravity, and based on the following evaluation criteria. Then, the specific bending strength of the cured product was evaluated.
[Evaluation criteria for specific bending strength]
A: Specific gravity is 1.41 g / cm ³ or less and specific bending strength is 30.0 MPa or more. O: Specific gravity is 1.41 g / cm ³ or less and specific bending strength is 29.3 MPa or more. Δ: The specific gravity is 1.41 g / cm ³ or more and the specific bending strength is 29.3 MPa or more. X: The specific bending strength is 29.3 MPa or less.

<Comprehensive evaluation>
Using the evaluation results of the laser speed and specific bending strength, the cured product was comprehensively evaluated based on the evaluation criteria of the following comprehensive evaluation. In addition, in the evaluation criteria of the following comprehensive evaluation, it can be practically used as a cured product with an evaluation of “◎” or “○”, but a cured product with an evaluation of “△” or “×” cannot be used practically. Become.
[Evaluation criteria for comprehensive evaluation]
◎: Both of the evaluation results of laser speed and specific bending strength are “◎” ○: Among the evaluation results of laser speed and specific bending strength, the lowest evaluation is “◯” △: Laser speed and specific bending strength Among the evaluation results, the lowest evaluation is “△”. ×: Among the evaluation results of laser speed and specific bending strength, the lowest evaluation is “×”.

  The evaluation results for Examples 1 to 25 and Comparative Examples 1 to 12 are shown in Table 8.

Aspects of the present invention are as follows, for example.
<1> A curable composition that is cured by light having a wavelength of 350 nm to 420 nm,
The curable composition includes a polymerizable compound and a filler,
The filler includes a light transmissive filler that transmits 75% or more of the light, and a light blocking filler that blocks 40% or more of the light,
At least one kind of the filler is a curable composition characterized by being an organic filler.
<2> The said curable composition is a curable composition as described in said <1> containing a polymerization initiator.
<3> The said polymerization initiator is a curable composition as described in said <2> which is a radical polymerization initiator.
<4> The curable composition according to any one of <1> to <3>, wherein the filler is included in a volume ratio of 10% to 50% with respect to a total amount of the curable composition.
<5> The curable composition according to <4>, wherein the filler is contained in a volume ratio of 20% to 40% with respect to a total amount of the curable composition.
<6> a light-transmitting filler that transmits 75% or more of light having a wavelength of 350 nm to 420 nm, and a light-blocking filler that blocks 40% or more of the light,
At least one of the fillers is a cured product characterized by being an organic filler.
<7> The cured product according to <6>, wherein the specific bending strength is 30 MPa or more.
<8> a supplying step of supplying the curable composition on or under the stage;
A curing step of curing at least a part of the supplied curable composition by irradiating light having a wavelength of 350 nm to 420 nm,
The curable composition is a curable composition according to any one of <1> to <5>, wherein the cured product is produced.
<9> Supply means for supplying the curable composition on or under the stage;
Curing means for curing at least a part of the supplied curable composition by irradiating light having a wavelength of 350 nm to 420 nm;
The curable composition is a curable composition according to any one of <1> to <5>, wherein the curable composition is an apparatus for producing a cured product.

  The curable composition according to any one of <1> to <5>, the cured product according to any one of <6> to <7>, the method for producing the cured product according to <8>, According to the manufacturing apparatus of the hardened | cured material as described in <9>, the said conventional problems can be solved and the objective of the said this invention can be achieved.

Japanese Patent No. 5605589 Japanese Patent No. 5774825 JP-A-10-101754 Japanese Patent No. 3971412 International Publication No. 2016/076180 International Publication No. 2016/114031

10 stage 20 curable composition 30 light 40 cured product

Claims (9)

A curable composition that is cured by light having a wavelength of 350 nm to 420 nm,
The curable composition includes a polymerizable compound and a filler,
The filler includes a light transmissive filler that transmits 75% or more of the light, and a light blocking filler that blocks 40% or more of the light,
A curable composition, wherein at least one of the fillers is an organic filler.   The said curable composition is a curable composition of Claim 1 containing a polymerization initiator.   The curable composition according to claim 2, wherein the polymerization initiator is a radical polymerization initiator.   The curable composition according to any one of claims 1 to 3, wherein the filler is contained in a volume ratio of 10% to 50% with respect to a total amount of the curable composition.   The curable composition according to claim 4, wherein the filler is contained in a volume ratio of 20% to 40% with respect to the total amount of the curable composition. A light-transmitting filler that transmits 75% or more of light having a wavelength of 350 nm to 420 nm, and a light-blocking filler that blocks 40% or more of the light,
At least one of the light transmissive filler and the light blocking filler is an organic filler.   The cured product according to claim 6, wherein the specific bending strength is 30 MPa or more. Supplying a curable composition above or below the stage;
A curing step of curing at least a part of the supplied curable composition by irradiating light having a wavelength of 350 nm to 420 nm,
The said curable composition is the curable composition in any one of Claim 1 to 5, The manufacturing method of the hardened | cured material characterized by the above-mentioned. Supply means for supplying the curable composition above or below the stage;
Curing means for curing at least a part of the supplied curable composition by irradiating light having a wavelength of 350 nm to 420 nm;
The said curable composition is the curable composition in any one of Claim 1 to 5, The manufacturing apparatus of the hardened | cured material characterized by the above-mentioned.