JP2020073333A - Resin components for three-dimensional modeling - Google Patents

Abstract

To provide resin compositions for three-dimensional modeling that can accurately produce three-dimensional modeling objects that can match the coefficient of thermal expansion with that of the peripheral members when used for the component parts of various devices.SOLUTION: This invention is a resin composition for three-dimensional modeling that contains a curable resin and a glass filler, and wherein the glass filler has a coefficient of thermal expansion of 60×10/°C or less at -40°C to 50°C, and the content of SiOas the composition is 90 mass% or less.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for three-dimensional modeling and a method for producing a three-dimensional molded article using the resin composition.

  BACKGROUND ART Conventionally, a method of obtaining a three-dimensional object by laminating resin materials and the like is known. For example, various methods such as a stereolithography method, a powder bed fusion sintering method, and a hot melt deposition (Fused deposition modeling: FDM) method have been proposed and put to practical use (see, for example, Patent Document 1).

  Among them, the stereolithography method is widely used because it is excellent in fine modeling and accurate size expression. The stereolithography method is a method for producing a three-dimensional object as follows. First, a molding stage is provided in a tank filled with a liquid photocurable resin, and the photocurable resin on the molding stage is irradiated with an active energy ray such as an ultraviolet laser to form a cured layer having a desired pattern. In this way, when one cured layer is formed, the molding stage is lowered by one layer, the uncured photocurable resin is introduced onto the cured layer, and the active energy ray is similarly irradiated to the photocurable resin. A new cured layer is stacked on the cured layer. By repeating this operation, a predetermined three-dimensional object is obtained. Further, in the powder sintering method, a molding stage is provided in a tank filled with resin, metal, ceramics or glass powder, the active energy ray is irradiated to the powder on the molding stage, and the desired pattern is cured by softening deformation. It forms a layer.

JP-A-7-26060

  When the three-dimensional model obtained by the above method is used, for example, as a component of various measuring devices or temperature controllers, it is required to match the coefficient of thermal expansion with peripheral members (for example, metal). In addition, many such parts have complicated shapes, and it is difficult to manufacture them with high accuracy by the above method.

  In view of the above, the present invention is a resin for three-dimensional modeling capable of accurately manufacturing a three-dimensional molded article that can match the thermal expansion coefficient with peripheral members when used as a component of various devices. It is intended to provide a composition.

The resin composition for three-dimensional modeling of the present invention is a resin composition for three-dimensional modeling containing a curable resin and a glass filler, wherein the glass filler has a heat of 60 × 10 ⁻⁷ / ° C. or less at −40 to 50 ° C. It is characterized by having a coefficient of expansion and having a SiO ₂ content of 90 mass% or less as a composition.

Generally, a resin has a large coefficient of thermal expansion and a large dimensional deformation due to temperature change. On the other hand, since the resin composition for three-dimensional modeling of the present invention contains a glass filler having a low thermal expansion coefficient of 60 × 10 ⁻⁷ / ° C. or less, dimensional deformation of the resin composition can be suppressed and the obtained three-dimensional structure can be obtained. The shaped article has high dimensional stability.

By the way, if the content of the filler in the resin composition is increased for the purpose of increasing the mechanical strength of the obtained three-dimensional molded article, the fluidity of the resin composition is lowered, and thus the three-dimensional molding having a complicated shape is performed. It becomes difficult to manufacture things with high precision. However, in the present invention, since a glass filler having a SiO ₂ content of 90% by mass or less is used as a filler, it is possible to easily mold the resin composition into a shape such as a spherical shape that does not deteriorate the fluidity. Therefore, even when a large amount is contained in the resin composition, a three-dimensional molded item can be accurately manufactured.

  In the resin composition for three-dimensional modeling of the present invention, the specific surface area of the glass filler is preferably 3 times or less than the theoretical specific surface area represented by the following formula.

Theoretical specific surface area (m ² / g) = 6 / (density (g / cm ³ ) × average particle size D50 (μm))

The theoretical specific surface area is a specific surface area when it is assumed that the glass filler has a spherical shape having a diameter of the average particle diameter D ₅₀ . If the specific surface area of the glass filler is specified as small as 3 times or less of the theoretical specific surface area, the irregularities on the surface of the glass filler are small and the fluidity of the resin composition is easily improved.

  In the three-dimensional modeling resin composition of the present invention, the glass filler is preferably substantially spherical. This makes it easier to improve the fluidity of the resin composition.

In stereolithography resin composition of the present invention, the glass filler is, by mass% as a _{composition, SiO 2 30~85%, Al 2} O 3 0~30%, B 2 O 3 0~50%, Li 2 O + Na 2 It is preferable to contain 0.01 to 10% of O + K ₂ O. With this, the softening point of the glass filler is lowered, and the moldability is easily improved. Here, “Li ₂ O + Na ₂ O + K ₂ O” means the total content of the components.

In stereolithography resin composition of the present invention, the glass filler is, by mass% as a _{composition, SiO 2 55~75%, Al 2} O 3 15~30%, Li 2 O 2~10%, Na 2 O 0~ 3%, K ₂ O 0 to 3%, MgO 0 to 5%, ZnO 0 to 10%, BaO 0 to 5%, TiO ₂ 0 to 5%, ZrO ₂ 0 to 4%, P ₂ O ₅ 0 to 5 %, And SnO ₂ 0 to 2.5% are preferably contained. By doing so, the thermal expansion coefficient of the glass filler can be easily lowered.

  In the resin composition for three-dimensional modeling of the present invention, the content of lead, mercury, chromium, cadmium, fluorine and arsenic in the glass filler is preferably 0.01% by mass or less. By doing so, it is possible to obtain an environmentally preferable three-dimensional object.

  In the three-dimensional modeling resin composition of the present invention, the softening point of the glass filler is preferably 1200 ° C. or lower. By doing so, it becomes possible to easily form a spherical shape or the like.

  In the three-dimensional modeling resin composition of the present invention, it is preferable that the glass filler has a light transmittance of 5% or more at a wavelength of 400 nm. By doing so, when the stereolithography method is applied, the active energy rays are easily spread inside the resin composition, and the production efficiency is easily improved.

  In the resin composition for three-dimensional modeling of the present invention, it is preferable that the glass filler deposits crystals (crystallized glass). By doing so, the coefficient of thermal expansion of the glass filler can be reduced. Therefore, the thermal expansion coefficient of the obtained three-dimensional model is also lowered, and the dimensional stability can be improved.

  In the resin composition for three-dimensional modeling of the present invention, a photocurable resin or a thermosetting resin can be used as the curable resin.

  It is preferable that the resin composition for three-dimensional modeling of the present invention contains a curable resin of 30 to 99% and a glass filler of 1 to 70% by volume.

  The method for producing a three-dimensional molded article of the present invention, a liquid layer comprising a resin composition is selectively irradiated with active energy rays to form a cured layer having a predetermined pattern, and a new liquid layer is formed on the cured layer. A method for producing a three-dimensional object which, after being formed, irradiates an active energy ray to form a new hardened layer having a predetermined pattern continuous with the hardened layer and repeats lamination of the hardened layer until a predetermined three-dimensional object is obtained. And, as the resin composition, the above-mentioned three-dimensional modeling resin composition is used.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for three-dimensional modeling which can manufacture a three-dimensional molded article which can match a thermal expansion coefficient with a peripheral member accurately when it is used for the component parts of various apparatuses. Can be provided.

  The three-dimensional modeling resin composition of the present invention contains a curable resin and a glass filler. The content ratio of each is preferably 30% to 99% of curable resin and 1% to 70% of glass filler in terms of volume%. More preferably, the curable resin is 35 to 95%, 40 to 90%, particularly 45 to 85%, and the glass filler is 5 to 65%, 10 to 60%, and particularly 15 to 55%. If the content of the glass filler is too small, it becomes difficult to obtain the effect of improving the mechanical strength. On the other hand, when the content of the glass filler is too large, the contact area of each glass filler particle with the curable resin is small, and the mechanical strength of the obtained three-dimensional molded article tends to be low. Further, in the case of the optical molding method, the viscosity of the resin composition becomes too high, which makes it difficult to form a new liquid layer on the molding stage.

  The curable resin used in the present invention may be either a photocurable resin or a thermosetting resin, and can be appropriately selected depending on the modeling method adopted. For example, a liquid photocurable resin may be selected when the stereolithography method is used, and a powdery thermosetting resin may be selected when the powder sintering method is employed.

  As the photocurable resin, various resins such as polymerizable vinyl compounds and epoxy compounds can be selected. Monomers and oligomers of monofunctional compounds and polyfunctional compounds are also used. These monofunctional compounds and polyfunctional compounds are not particularly limited. Typical examples of the photocurable resin are given below.

  Examples of the monofunctional compound of a polymerizable vinyl compound include isobornyl acrylate, isobornyl methacrylate, zinc pentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and propylene glycol. Examples thereof include acrylate, vinylpyrrolidone, acrylamide, vinyl acetate and styrene. As the polyfunctional compound, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate, diallyl phthalate and the like. One or more of these monofunctional compounds and polyfunctional compounds can be used alone or in the form of a mixture.

  A photopolymerization initiator is used as the polymerization initiator for the vinyl compound. As the photopolymerization initiator, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, Michler's ketone and the like can be mentioned as a typical example, and these initiators can be used alone or in combination of two or more kinds. If necessary, a sensitizer such as an amine compound may be used in combination. The amount of each of these polymerization initiators used is preferably 0.1 to 10% by mass based on the vinyl compound.

  Examples of epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4. -Epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate and the like. When using these epoxy compounds, an energy active cation initiator such as triphenylsulfonium hexafluoroantimonate can be used.

  Further, a leveling agent, a surfactant, an organic polymer compound, an organic plasticizer, etc. may be added to the photocurable resin, if necessary.

The glass filler used in the present invention has a coefficient of thermal expansion of 60 × 10 ⁻⁷ / ° C. or less at −40 to 50 ° C., and has a SiO ₂ content of 90 mass% or less as a composition. To do. Thereby, the thermal expansion coefficient of the obtained three-dimensional molded item can be reduced, and at the same time, the resin composition can be easily molded into a shape such as a spherical shape that does not deteriorate the fluidity of the resin composition. Hereinafter, the specific composition of the glass filler will be described. In the following description regarding the content of each component, “%” represents mass% unless otherwise specified.

(Glass composition A)
As the glass filler, in mass% as a _composition, those containing _{SiO 2 30~85%, Al 2 O} 3 0~30%, B 2 O 3 0~50%, the 2 O 0~10% Li 2 O + Na 2 O + K Can be used. The reason for limiting the glass composition in this way will be described below.

SiO ₂ is a component that forms a glass skeleton, and has an effect of easily improving chemical durability and suppressing devitrification. The content of SiO ₂ is preferably 30 to 85%, 40 to 75%, and particularly preferably 45 to 70%. If the amount of SiO ₂ is too small, it becomes difficult to obtain the above effect. On the other hand, when the amount of SiO ₂ is too large, the softening point tends to be high and the moldability tends to be poor.

Al ₂ O ₃ is a vitrification-stable component. It also has a high effect of improving chemical durability. The content of Al ₂ O ₃ is preferably 0 to 30%, 2.5 to 25%, and particularly preferably 5 to 20%. If the amount of Al ₂ O ₃ is too large, the softening point rises and it becomes difficult to mold. In addition, meltability and chemical durability are likely to be lowered, and devitrification is likely to occur.

B ₂ O ₃ is a component that forms a glass skeleton. Further, it has the effect of easily improving chemical durability and suppressing devitrification. The content of B ₂ O ₃ is preferably 0 to 50%, 2.5 to 40%, and particularly 5 to 30%. When the content of B ₂ O ₃ is too large, the meltability is lowered, and it becomes difficult to soften during molding, which makes manufacturing difficult.

Li ₂ O, Na ₂ O and K ₂ O are components that lower the softening point and facilitate molding. The content of Li ₂ O + Na ₂ O + K ₂ O is preferably 0 to 10%, 0.01 to 9%, 0.1 to 8%, and particularly preferably 1 to 7%. If the amount of Li ₂ O + Na ₂ O + K ₂ O is too large, the thermal expansion coefficient tends to be large and the chemical durability tends to be low. The content of each component of Li ₂ O, Na ₂ O and K ₂ O is also preferably set in the above range.

  The glass filler may contain the following components in addition to the above components.

  MgO, CaO, SrO, BaO and ZnO are components that reduce the viscosity without greatly reducing the chemical durability. The total content of these components is preferably 0 to 50%, 0.1 to 50%, 1 to 40%, and particularly 2 to 30%. When the content of these components is too large, devitrification tends to occur.

P ₂ O ₅ is a component that forms a glass skeleton, and it is easy to improve light transmittance and chemical durability, and also has an effect of suppressing devitrification. The content of P ₂ O ₅ is preferably 0 to 50%, 2.5 to 40%, and particularly preferably 5 to 30%. If the amount of P ₂ O ₅ is too large, the meltability tends to decrease. In addition, the weather resistance is likely to decrease. On the other hand, if P ₂ O ₅ is too small, devitrification is likely to occur.

(Glass composition B)
As the glass filler, the composition is mass%, and SiO ₂ 55 to 75%, Al ₂ O ₃ 15 to 30%, Li ₂ O 2 to 10%, Na ₂ O 0 to 3%, K ₂ O 0 to 3%. _{, 0~5% MgO, 0~10% ZnO} , BaO 0~5%, TiO 2 0~5%, ZrO 2 0~4%, P 2 O 5 0~5%, and _SnO 2 0 to 2.5 % Can be used. The glass filler having the above composition has a property of precipitating a β-quartz solid solution and / or β-eucryptite having a low expansion property when heated at a temperature above the crystallization start temperature.

  The reason for limiting the glass composition as described above will be described below.

SiO ₂ forms a glass skeleton and also serves as a constituent component of crystals. The content of SiO ₂ is preferably 55 to 75%, particularly preferably 60 to 75%. If the amount of SiO ₂ is too small, the coefficient of thermal expansion tends to be high and the chemical durability tends to be low. On the other hand, if the amount of SiO ₂ is too large, the meltability tends to decrease. Further, the viscosity of the molten glass becomes large, and fining and molding tend to be difficult.

Al ₂ O ₃ forms a glass skeleton and also serves as a constituent component of crystals. The content of Al ₂ O ₃ is preferably 15 to 30%, particularly preferably 17 to 27%. When the amount of Al ₂ O ₃ is too small, the coefficient of thermal expansion tends to be high and the chemical durability tends to be low. On the other hand, when Al ₂ O ₃ is too much, the meltability tends to decrease. Further, the viscosity of the molten glass becomes large, and fining and molding tend to be difficult. Furthermore, it becomes easier to devitrify.

Li ₂ O is a constituent component of crystals and is a component that greatly affects the crystallinity and reduces the viscosity to improve the meltability and moldability. The content of Li ₂ O is preferably 2 to 10%, 2 to 7%, 2 to 5%, and particularly 2 to 4.8%. If the content of Li ₂ O is too small, it becomes difficult for crystals to precipitate, or the meltability tends to decrease. In addition, the viscosity tends to increase, and fining and molding tend to be difficult. On the other hand, when the content of Li ₂ O is too large, devitrification is likely to occur.

Na ₂ O and K ₂ O are components for lowering the viscosity and improving the meltability and moldability. The content of Na ₂ O and K ₂ O is preferably 0 to 3%, particularly preferably 0.1 to 1%. If the content of Na ₂ O or K ₂ O is too large, devitrification tends to occur and the coefficient of thermal expansion tends to increase. Further, when the glass filler is mixed with the resin, the resin may deteriorate.

  MgO is a component for adjusting the thermal expansion coefficient. The content of MgO is preferably 0 to 5%, 0.1 to 3%, and more preferably 0.3 to 2%. If the content of MgO is too large, devitrification is likely to occur and the coefficient of thermal expansion tends to be high.

  ZnO is a component for adjusting the thermal expansion coefficient. The ZnO content is preferably 0 to 10%, 0 to 7%, 0 to 3%, and particularly preferably 0.1 to 1%. If the ZnO content is too high, devitrification tends to occur.

  BaO is a component for lowering the viscosity and improving the meltability and moldability. The content of BaO is preferably 0 to 5%, particularly preferably 0.1 to 3%. If the content of BaO is too large, devitrification tends to occur.

TiO ₂ and ZrO ₂ are components that act as a nucleating agent for precipitating crystals in the crystallization process. The content of TiO ₂ is preferably 0 to 5%, particularly preferably 1 to 4%. The ZrO ₂ content is preferably 0 to 4%, particularly preferably 0.1 to 3%. If the content of TiO ₂ or ZrO ₂ is too large, devitrification tends to occur.

P ₂ O ₅ is a component that promotes phase separation and helps formation of crystal nuclei. The content of P ₂ O ₅ is preferably 0 to 5%, particularly preferably 0.1 to 4%. If the content of P ₂ O ₅ is too large, the phases are excessively separated, and the light transmittance is likely to decrease.

SnO ₂ is a component that acts as a fining agent. The SnO ₂ content is preferably 0 to 2.5%, particularly preferably 0.1 to 2%. When the content of SnO ₂ is too large, devitrification tends to occur, or the light transmittance tends to decrease.

In addition to the above components, B ₂ O ₃ , CaO, SrO and the like can be appropriately contained within a range that does not impair the effects of the present invention.

In addition, in each of the glass composition A and the glass composition B, the content of lead, mercury, chromium, cadmium, fluorine and arsenic in the glass composition should be 0.01% by mass or less for environmental reasons. preferable. Further, from the viewpoint of suppressing a decrease in light transmittance, the total content of Fe ₂ O ₃ , NiO and CuO in the glass composition is 1% or less, 0.75% or less, and particularly 0.5% or less. Is preferred, and the total content of TiO ₂ , WO ₃ , La ₂ O ₃ , Gd ₂ O _3, and Bi ₂ O ₃ is 5% or less, 2.5% or less, and particularly preferably 1% or less. ..

The thermal expansion coefficient of the glass filler of the present invention at −40 to 50 ° C. is 60 × 10 ⁻⁷ / ° C. or less, preferably 50 × 10 ⁻⁷ / ° C. or less, and particularly preferably 40 × 10 ⁻⁷ / ° C. or less. .. If the coefficient of thermal expansion of the glass filler is too high, it becomes difficult to obtain the effect of reducing the coefficient of thermal expansion of the obtained three-dimensional model. The glass filler having the above glass composition B achieves a low coefficient of thermal expansion of, for example, 5 × 10 ⁻⁷ / ° C. or less, 3 × 10 ⁻⁷ / ° C. or less, and particularly 2 × 10 ⁻⁷ / ° C. or less by crystal precipitation. It is possible to

  The specific surface area of the glass filler is preferably 3 times or less, 2.5 times or less, and more preferably 2 times or less the theoretical specific surface area represented by the following formula. By doing so, the irregularities on the surface of the glass filler are small, and the fluidity of the resin composition can be easily improved. By subjecting the glass filler to processing such as fire polishing, the surface roughness can be reduced and the specific surface area can be reduced. The shape of the glass filler is not particularly limited, but it is preferably substantially spherical from the viewpoint of reducing the specific surface area.

Theoretical specific surface area (m ² / g) = 6 / (density (g / cm ³ ) × average particle diameter D ₅₀ (μm))

The specific surface area of the glass filler is preferably 0.1 to ⁵ m ² / g, 0.5 to ⁴ m ² / g, and particularly preferably 0.75 to ³ m ² / g. If the specific surface area of the glass filler is too small, the particle size tends to increase, and the fluidity of the resin composition tends to decrease. On the other hand, when the specific surface area of the glass filler is too large, the fluidity of the resin composition is lowered and the interfacial bubbles are hard to come off. In addition, the mechanical strength of the obtained three-dimensional model is likely to decrease.

The average particle diameter D ₅₀ of the glass filler is preferably 1 to ₅₀₀ μm, 1.5 to 100 μm, 2 to ₅₀ μm, and particularly preferably 2.5 to 20 μm. The smaller the average particle diameter D ₅₀ of the glass filler is, the higher the filling rate can be, but the fluidity of the curable resin tends to decrease, and the interfacial bubbles tend not to come out easily. On the other hand, the larger the average particle diameter D ₅₀ of the glass filler is, the more easily the filling rate is lowered.

In the present invention, the average particle diameter D ₅₀ represents the 50% volume cumulative diameter of the median diameter of primary particles, and is a value measured by a laser diffraction type particle size distribution measuring device.

  The light transmittance of the glass filler at a wavelength of 400 nm is preferably 5% or more, 10% or more, 30% or more, 50% or more, and particularly preferably 70% or more. Particularly in the case of the stereolithography method, if the light transmittance of the glass filler at a wavelength of 400 nm is too low, the active energy rays are less likely to enter the inside of the resin composition and hard to cure.

The density of the glass filler is not particularly limited and may be appropriately adjusted according to the intended use. For example, the density of the glass filler is preferably adjusted appropriately in the range of 2.4 to ⁴ g / cm ³ , and particularly 2.5 to 3.5 g / cm ³ .

  The refractive index nd and the Abbe's number νd of the glass filler are not particularly limited and may be appropriately adjusted according to the resin used. For example, it is preferable to appropriately adjust the refractive index nd of the glass filler within the range of 1.40 to 1.75 and the Abbe number νd within the range of 30 to 70.

  The surface of the glass filler is preferably treated with a silane coupling agent. By treating with a silane coupling agent, the binding force between the glass filler and the curable resin can be increased, and it becomes possible to obtain a three-dimensional molded article having more excellent mechanical strength. In addition, the compatibility between the glass filler and the curable resin is improved, and interface bubbles can be reduced. Furthermore, the weather resistance of the glass filler can be improved. As the silane coupling agent, for example, aminosilane, epoxysilane, acrylsilane and the like are preferable. The silane coupling agent may be appropriately selected depending on the curable resin used. For example, when a vinyl unsaturated compound is used as the photocurable resin, an acrylic silane silane coupling agent is most preferable, and an epoxy compound is used. When used, it is desirable to use an epoxysilane-based silane coupling agent.

Further, oxide nanoparticles may be contained in the resin composition at a ratio of 1% by volume or less for the purpose of improving mechanical strength. As the oxide nanoparticles, ZrO ₂ , Al ₂ O _3, SiO ₂ or the like can be used. These oxide nanoparticles also have the effect of improving the wettability of the glass filler with the resin and reducing the viscosity of the resin composition. The average particle diameter of the oxide nanoparticles is preferably 1 to 1000 nm, 2.5 to 750 nm, and particularly preferably 5 to 500 nm. If the average particle size of the oxide nanoparticles is too small, it is difficult to obtain the effect of improving the mechanical strength. If the average particle diameter of the oxide nanoparticles is too large, it becomes difficult to obtain the effect of reducing the viscosity of the resin composition. Further, the light transmittance of the resin composition is likely to decrease due to the scattering caused by the difference in the refractive index with the resin.

  Next, an example of the manufacturing method of the three-dimensional molded object of the present invention will be described. Specifically, a method for producing a three-dimensional object using a resin composition containing a photocurable resin will be described. The resin composition is as described above, and the description is omitted here.

  First, one liquid layer made of a photocurable resin composition is prepared. For example, a modeling stage is provided in a tank filled with a liquid photocurable resin composition, and the stage upper surface is positioned so as to have a desired depth (for example, about 0.2 mm) from the liquid surface. By doing so, a liquid layer can be prepared on the stage.

  Next, the liquid layer is irradiated with an active energy ray, for example, an ultraviolet laser to cure the photocurable resin to form a cured layer having a predetermined pattern. As the active energy ray, laser light such as visible light or infrared light can be used in addition to ultraviolet light.

  Then, a new liquid layer made of a photocurable resin composition is prepared on the formed cured layer. For example, it is possible to prepare a new liquid layer by introducing the photocurable resin onto the cured layer by lowering the modeling stage by one layer.

  Then, a new liquid layer prepared on the hardened layer is irradiated with an active energy ray to form a new hardened layer continuous with the hardened layer.

  By repeating the above operation, the cured layers are continuously laminated to obtain a predetermined three-dimensional model.

  The three-dimensional object obtained by the manufacturing method of the present invention is suitable as a positioning member of various measuring devices, a component of a temperature controller, and the like.

  Below, the resin composition for three-dimensional modeling of this invention is demonstrated based on an Example. Table 1 shows examples and comparative examples of the present invention.

(Preparation of photocurable resin)
First, isophorone diisocyanate, morpholine acrylamide and dibutyltin dilaurate were heated in an oil bath. Next, a liquid in which methylhydroquinone was uniformly mixed and dissolved in glycerin monomethacrylate monoacrylate was put, and the mixture was reacted by stirring and mixing. Further, by adding 4 moles of propylene oxide of pentaerythritol (one mole of propylene oxide added to each of the four hydroxyl groups of pentaerythritol) and reacting, a reaction product containing a urethane acrylate oligomer and morpholine acrylamide is obtained. It was made.

  Morpholine acrylamide and dicyclopentanyl diacrylate were added to the obtained reaction product. Further, 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) was added to obtain a colorless and transparent acrylic photocurable resin. The acrylic photocurable resin had a viscosity of 1 Pa · s and a refractive index nd after curing of 1.5103.

(Preparation of glass filler)
First, raw materials were prepared so as to have the composition shown in Table 1 and melted at 1500 to 1600 ° C. for 4 to 8 hours. The molten glass was molded into a film with a molding roller and then pulverized to prepare a glass powder having an average particle diameter D ₅₀ of 5 μm. The obtained glass powder was applied to the frame of an oxygen burner and molded into a spherical shape. Then, classification was performed to obtain a glass filler (glass beads) having an average particle diameter D ₅₀ of 5 μm. Each characteristic of the obtained glass filler was measured by the following methods.

  The softening point was measured using the fiber elongation method.

  The density was measured by the Archimedes method.

  The refractive index nd and the Abbe number νd were measured using a precision refractometer (KPR-2000 manufactured by Shimadzu Device).

  The light transmittance at a wavelength of 400 nm was measured using a spectrophotometer (UV-3100 manufactured by Shimadzu Corp.) by preparing a sample having a thickness of 1 mm ± 0.01 mm and mirror-polished on both sides.

  The thermal expansion coefficient was measured using a dilatometer.

(Preparation of resin composition for stereolithography)
The photocurable resin and the glass filler were weighed to be 70% by volume and 30% by volume, respectively, and kneaded with three rollers to obtain a paste-like resin composition in which the glass filler was homogeneously dispersed. ..

  The obtained paste resin composition was poured into a mold made of Teflon (registered trademark) and having an inner size of 30 mm □. Then, after irradiating with light of 500 mW and a wavelength of 364 nm for 10 seconds, it was annealed at 80 ° C. to obtain a three-dimensional object. The thermal expansion coefficient of the obtained three-dimensional model was measured. The results are shown in Table 1.

As is clear from Table 1, the three-dimensional shaped objects of Examples 1 and 2 had a thermal expansion coefficient of 690 × 10 ⁻⁷ / ° C. or less. On the other hand, the thermal expansion coefficient of Comparative Examples 1 and 2 was as high as 750 × 10 ⁻⁷ / ° C. or higher.

Claims (11)

A three-dimensional modeling resin composition containing a curable resin and a glass filler,
The glass filler has a coefficient of thermal expansion of 60 × 10 ⁻⁷ / ° C. or less at −40 to 50 ° C., and the content of SiO ₂ as a composition is 90 mass% or less,
An average particle diameter D ₅₀ of the glass filler is 1.5 to ₅₀ μm. The resin composition for three-dimensional modeling according to claim 1, wherein the specific surface area of the glass filler is 3 times or less of the theoretical specific surface area represented by the following formula.
Theoretical specific surface area (m ² / g) = 6 / (density (g / cm ³ ) × average particle size D50 (μm))   The three-dimensional resin composition according to claim 1 or 2, wherein the glass filler has a substantially spherical shape. The glass filler contains SiO ₂ 30 to 85%, Al ₂ O ₃ 0 to 30%, B ₂ O ₃ 0 to 50%, Li ₂ O + Na ₂ O + K ₂ O 0.01 to 10% in terms of composition by mass%. The resin composition for three-dimensional modeling according to any one of claims 1 to 3, characterized in that. The composition of the glass filler in mass% is SiO ₂ 55 to 75%, Al ₂ O ₃ 15 to 30%, Li ₂ O 2 to 10%, Na ₂ O 0 to 3%, K ₂ O 0 to 3%, _{0~5% MgO, 0~10% ZnO,} BaO 0~5%, TiO 2 0~5%, ZrO 2 0~4%, P 2 O 5 0~5%, and _SnO 2 0 to 2.5% The resin composition for three-dimensional modeling according to any one of claims 1 to 3, further comprising:   The content of lead, mercury, chromium, cadmium, fluorine, and arsenic in the glass filler is 0.01% by mass or less, respectively, and the three-dimensional modeling resin according to any one of claims 1 to 5. Composition.   The softening point of the glass filler is 1200 ° C or lower, and the resin composition for three-dimensional modeling according to any one of claims 1 to 6.   The resin composition for three-dimensional modeling according to any one of claims 1 to 7, wherein the glass filler has a light transmittance of 5% or more at a wavelength of 400 nm.   The resin composition for three-dimensional modeling according to any one of claims 1 to 8, wherein the glass filler deposits crystals.   The curable resin is a photocurable resin or a thermosetting resin, The three-dimensional modeling resin composition according to claim 1, wherein the curable resin is a photocurable resin or a thermosetting resin.   A liquid layer made of a resin composition is selectively irradiated with an active energy ray to form a cured layer having a predetermined pattern, and a new liquid layer is formed on the cured layer, and then an active energy ray is irradiated to form the cured layer. A method for producing a three-dimensional model, comprising forming a new cured layer having a predetermined pattern continuous with the cured layer, and repeating the lamination of the cured layer until a predetermined three-dimensional model is obtained, which is a resin composition. A method for producing a three-dimensional object, comprising using the resin composition for three-dimensional object according to any one of 1 to 10.