JPH0820620A - Resin composition for optical three-dimensional molding - Google Patents

Abstract

PURPOSE:To obtain a composition having viscosity suitable for a molding, capable of preparing a stable liquid free from settling of fine particles, forming an optical three-dimensional molding having sufficiently high mechanical characteristics and low volume shrinkage ratio. CONSTITUTION:This resin composition for optical three-dimensional molding contains a liquid optically curable resin, solid fine particles and whiskers, has the ratio of the solid fine particles to the whiskers of (14-1):(6-1), the solid fine particles have 3-70mum average particle diameter and the whiskers have 0.3-1mum diameters, 10-70mum length and 100-100 aspect ratio. The ratio of inorganic solid fine particles to organic polymer solid fine particles is 1:9 to 9:1. The inorganic polymer solid fine particles are glass beads, talc fine particles or silicon oxide fine particles. The organic polymer solid fine particles comprise a crosslinked polystyrene polymer, a crosslinked polymethacrylate polymer, a polyethylenic polymer or a polypropylene-based polymer. The whiskers comprise an aluminum borate-based compound, a basic magnesium sulfate-based compound, an aluminum oxide or an silicon oxide-based compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition for optical three-dimensional modeling, and particularly, it has a low volumetric shrinkage before and after curing, is excellent in dimensional accuracy, and has excellent mechanical properties and heat resistance. The present invention relates to a resin composition for optical three-dimensional modeling.

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 56-144478 discloses a method of supplying a three-dimensional object by supplying a required amount of light energy to a photocurable resin, and further, Japanese Unexamined Patent Publication (Kokai) No. 60- A basic practical method was proposed by Japanese Patent No. 247515. After that, similar or improved techniques are disclosed in JP-A-62-35966 and JP-A-1-20491.
5, JP-A-2-113925, JP-A-2-11325
145616, JP-A-2-153722,
It is disclosed in JP-A-3-15520, JP-A-3-21432, and JP-A-3-41126.

A typical example of the optical three-dimensional molding method is to selectively irradiate an ultraviolet laser controlled by a computer so that a desired pattern can be obtained on the liquid surface of a liquid photocurable resin contained in a container. By curing to a predetermined thickness, then supplying one layer of liquid resin on the cured layer, and similarly curing by irradiation with an ultraviolet laser in the same manner as described above to obtain a continuous cured layer. This is a method of finally obtaining a three-dimensional object. This optical three-dimensional modeling method has recently attracted particular attention because it can be easily obtained in a relatively short time even if the shape of a modeled object to be manufactured is quite complicated.

Conventionally, the photocurable resin used in the optical three-dimensional molding method includes modified polyurethane (meth) acrylate, oligoester acrylate, urethane acrylate, epoxy acrylate, photosensitive polyimide, aminoalkyd and the like. Also, recently, JP-A-1
-204915, Japanese Patent Application Laid-Open No. 1-213304, Japanese Patent Application Laid-Open No. 2-28261, Japanese Patent Application Laid-Open No. 2-7561.
7, JP-A-2-145616, JP-A-3-
Various improved techniques are disclosed in JP-A-104626, JP-A-3-114732, JP-A-3-114733 and the like.

[0004]

In the optical three-dimensional molding method, the photocurable resin used is easy to handle,
From the viewpoint of molding speed, molding accuracy, etc., the resin viscosity is relatively low, the volumetric shrinkage rate during curing is low from the viewpoint of dimensional accuracy of the molded product, and the mechanical properties of the obtained molded product are sufficiently high. Not only is it required, but recently, high heat resistance is required depending on the application. However,
None of the above-mentioned conventional liquid photocurable resins have been provided that are satisfactory in these characteristics and especially in dimensional accuracy.

Therefore, as a result of earnestly continuing to improve the above-mentioned various characteristics, the inventor of the present invention blended liquid photo-curable resin with predetermined organic polymer solid fine particles and / or inorganic solid fine particles, and It was found that not only the rigidity is remarkably improved but also the volumetric shrinkage rate is much lower than expected, and a patent application has been filed here, but as a result of further research, when whiskers were added to the solid fine particles, it was observed that the The present inventors have found that not only a stable liquid material can be obtained without sedimentation of solid fine particles, but also excellent mechanical rigidity and volume shrinkage can be obtained, and the present invention has been completed here. Therefore, the object of the present invention is to provide a resin composition for optical three-dimensional modeling which has a preferable viscosity in terms of modeling and handling and is stable for a long period of time, and further has sufficiently high mechanical properties and excellent heat resistance. Another object of the present invention is to provide a resin composition for optical three-dimensional modeling, which has a small volume shrinkage and therefore can provide a three-dimensional molded article excellent in dimensional accuracy.

[0006]

The above objects of the present invention can be achieved by the following inventions. (1) A resin composition for optical three-dimensional modeling, wherein the liquid photocurable resin contains solid fine particles and whiskers. (2) The ratio of solid fine particles and whiskers is 14 to 1: 6.
The resin composition for optical three-dimensional modeling as described in the above item 1, characterized in that (3) The solid fine particles have an average particle size of 3 to 70 μm, and the whiskers have a diameter of 0.3 μm to 1 μm and a length of 10 μm to 7
The resin composition for optical three-dimensional modeling according to any one of the above items 1 and 2, wherein the resin composition has a thickness of 0 μm and an aspect ratio of 10 to 100. (4) The resin composition for optical three-dimensional modeling according to any one of items 1 to 3, wherein the solid fine particles are inorganic solid fine particles and organic polymer solid fine particles. (5) The ratio of the inorganic solid fine particles and the organic polymer solid fine particles is 1: 9 to 9: 1, and the resin for optical three-dimensional modeling according to any one of items 1 to 4 above. Composition. (6) The inorganic solid fine particles are glass beads, talc fine particles,
The resin composition for optical three-dimensional modeling according to any one of items 1 to 5, wherein the resin composition is at least one selected from silicon oxide fine particles. (7) The organic polymer solid fine particles are at least one selected from cross-linked polystyrene-based polymers, cross-linked polymethacrylate-based polymers, polyethylene-based polymers and polypropylene-based polymers. Through sixth
Item 3. A resin composition for optical three-dimensional modeling according to any one of items. (8) The whisker comprises at least one of an aluminum borate-based compound, a basic magnesium sulfate-based compound, aluminum oxide and a silicon oxide-based compound. A resin composition for optical three-dimensional modeling. (9) The optical system according to any one of items 1 to 8, wherein the solid fine particles are treated with at least one silane coupling agent selected from aminosilane, epoxysilane, and acrylsilane. Resin composition for stereoscopic modeling. (10) The liquid photo-curable resin is mainly composed of an ethylenically unsaturated compound, and the solid fine particles are treated with an acrylsilane-based silane coupling agent. Item 10. A resin composition for optical three-dimensional modeling according to any one of items 9. (11) The above-mentioned items 1 to 10, wherein the liquid photocurable resin is mainly composed of an epoxy compound, and the solid fine particles are treated with an epoxysilane-based silane coupling agent. The resin composition for optical three-dimensional modeling according to any one of 1. (12) The optical solid according to any one of items 1 to 11, wherein the organic polymer solid fine particles are polyethylene solid fine particles obtained by copolymerizing 1 to 10% by weight of an acrylic acid compound. A resin composition for three-dimensional modeling.

The present invention will be described in more detail below. The resin composition for stereolithography of the present invention has the above-mentioned constitution and thus has a viscosity preferable for modeling and handling, and a stable liquid stereolithography for a long time. Therefore, the optical three-dimensional molded article obtained from this composition can hold the resin composition for use, has a small volume shrinkage, is excellent in dimensional accuracy, and has sufficiently high mechanical properties and heat resistance. Furthermore, the resin composition for stereolithography of the present invention is a resin containing whiskers, and the optical three-dimensional molded article obtained therefrom has not only excellent dimensional accuracy but also tensile strength,
Tensile elastic modulus, bending strength, bending elastic modulus are significantly improved,
And the heat resistance is improved.

The resin composition for optical three-dimensional modeling used in the present invention contains a mixed particle of solid fine particles and whiskers, and thus has a viscosity preferable for modeling and handling and is stable for a long time for liquid stereolithography. A resin composition capable of holding a resin composition and having excellent mechanical rigidity and heat resistance and a volumetric shrinkage ratio much smaller than expected can be obtained. Therefore, a three-dimensional molded object with further excellent dimensional accuracy can be obtained. To be In the present invention, this enables development of a wide range of new uses for optical three-dimensionally shaped objects. Here, in “having organic polymer solid fine particles and / or inorganic solid fine particles”, “and or” means the case where the organic polymer solid fine particles and the inorganic solid fine particles are present together and the case of the organic polymer solid fine particles and the inorganic solid fine particles. Of these, the term is used in the meaning of both of the cases where any one of them has one.

The organic polymer solid fine particles and / or the inorganic solid fine particles used in the present invention have an average particle diameter of 3 to 3, respectively.
It is 70 μm, preferably 10 to 60 μm, and more preferably 15 to 50 μm. In this case, the organic polymer solid fine particles and the inorganic solid fine particles may have the same particle diameter or different particle diameters, and preferably have the same particle diameter. When the average particle size of these solid fine particles is smaller than 3 μm, the resin viscosity is unnecessarily increased, and it cannot be blended in a desired ratio. On the other hand, when the average particle size is larger than 70 μm, irradiation is performed. At this time, the scattering of active energy occurs and the precision of the modeled object decreases. The whisker used in the present invention has a diameter (or width) of 0.3 μm to 1 μm, preferably 0.3 μm to 0.7 μm, and a length of 1
0 μm to 70 μm, preferably 20 μm to 50 μm
m. Further, the aspect ratio is 10 to 100, preferably 20 to 70.

When the aspect ratio of the whiskers used in the present invention is smaller than 10, the effect of the present invention when the whiskers are added, that is, the effect of particularly improving the mechanical strength and the effect of lowering the volume shrinkage cannot be obtained. It is not preferable because the viscosity of the resin only unnecessarily increases. On the other hand, if the aspect ratio of the whiskers is increased, the mechanical strength is improved and the volume contraction rate is lowered. However, if the aspect ratio exceeds 100, the viscosity of the resin becomes too high or the resin becomes too high. Not only makes the molding operation difficult, but also reduces the side accuracy of the modeled object. Therefore, there is a limit to the size of the aspect ratio, and the aspect ratio is preferably 100 or less, more preferably 70 or less. In the present invention, the mixing ratio of the solid fine particles and the whiskers is 14 to 1: 6-1, preferably 12 to 1: 5-1. Outside of this range, less favorable results cannot be obtained. The compounding ratio of the organic polymer solid fine particles and / or the inorganic solid fine particles used in the present invention is 5 to 70% by volume, respectively,
It is preferably 10 to 55% by volume. The blending ratio of these organic polymer solid fine particles and / or inorganic solid fine particles,
When the content is less than 5% by volume, the effect of the present invention is not sufficiently exhibited. On the other hand, when the content is more than 70% by volume, the viscosity of the resin composition for optical three-dimensional molding becomes too high. As a result, the mechanical strength of the obtained molded article is deteriorated, which is not preferable, and the molding operation is difficult, which is not preferable.

The viscosity of the resin composition for optical three-dimensional molding of the present invention is preferably 5,000 cps to 10 when organic polymer solid fine particles and / or inorganic solid fine particles are used.
A guideline is 10,000 cps. When whiskers are used, the viscosity of the resin composition for optical three-dimensional modeling of the present invention may be lower than that when the solid fine particles are used, and preferably 1,000 cps or more. In the present invention, the ratio of the organic polymer solid fine particles and the inorganic solid fine particles is 9: 1 when these are mixed.
It can be arbitrarily adjusted within the range of to 1: 9. It is preferably 8: 2 to 2: 8. The compounding ratio of the whisker used in the present invention to the liquid photocurable resin is 5 to 30.
%, Preferably 7 to 20% by volume. When the blending ratio of this whisker is less than 5% by volume, the effect of the present invention is not sufficiently exhibited, while the blending ratio is
If it exceeds 30% by volume, the viscosity of the resin composition for optical three-dimensional modeling becomes too high, which not only causes difficulty in use but also impedes the penetration of light, which causes problems in modeling operation and cannot be used. .

As the organic polymer solid fine particles used in the present invention, crosslinked polystyrene-based polymers, crosslinked polymethacrylate-based polymers, polyethylene-based polymers, polypropylene-based polymers and the like are mentioned as representatives of preferable ones. As the inorganic solid fine particles used in the present invention,
Glass beads, talc fine particles, silicon oxide fine particles and the like are mentioned as typical examples thereof, but examples of organic polymer solid fine particles and inorganic solid fine particles are not limited to these, and many others are used. The whisker used in the present invention comprises at least one of aluminum borate compounds, magnesium hydroxide sulfate compounds, aluminum oxide and silicon oxide compounds, preferably aluminum borate compounds, magnesium hydroxide sulfate compounds. It is a compound or an aluminum oxide type compound. In the present invention, it is preferable to contain whiskers in the optical three-dimensional modeling resin composition, particularly the liquid photocurable resin, but it may further contain organic polymer solid fine particles and / or inorganic solid fine particles as described above. Good. The organic polymer solid fine particles and / or inorganic solid fine particles or whiskers used in the present invention are preferably treated with a silane coupling agent, and organic polymer solid fine particles treated with such a silane coupling agent. When and / or inorganic solid fine particles or whiskers are used, preferable ones having particularly excellent mechanical strength can be obtained.

As the silane coupling agent used in the present invention, aminosilane, epoxysilane, acrylsilane and the like are preferably used. The effect of the type of the silane coupling agent varies depending on the liquid photocurable resin used. When a vinyl unsaturated compound is used as the liquid photocurable resin, an acrylic silane silane coupling agent is most preferable, and when an epoxy compound is used as the liquid photocurable resin, an epoxysilane silane coupling agent is used. It is most effective to use.
When polyethylene-based polymer, polypropylene-based polymer or the like is used as the organic polymer solid fine particles, at least 1 to 10% by weight, and preferably 5 to 8% by weight of the acrylic acid-based compound is used as the solid fine particles. It is possible to obtain preferable results by using a polymerized product. When the amount of the acrylic acid compound is less than 1% by weight, there is almost no effect of mechanical strength developed by the treatment with the silane coupling agent, and the amount of the acrylic acid compound is 10% by weight.
Even if it exceeds, the effect does not change much. The liquid photocurable resin used in the present invention may be any one of a polymerizable vinyl compound, an epoxy compound, a monofunctional compound,
Any monomers and / or oligomers of polyfunctional compounds can be used. These monofunctional compounds and polyfunctional compounds are not particularly limited, and typical liquid photocurable resins are listed below.

[Polymerizable Vinyl Compound] 1) As the monofunctional compound, isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2 -Hydroxypropyl acrylate, propylene glycol monoacrylate, vinylpyrrolidone, acrylamide, vinyl acetate, styrene and the like.

2) Polyfunctional compounds include trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, ethylene glycol diacrylate, diethylene 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 can be mentioned. One or more such monofunctional compounds and / or polyfunctional compounds can be used alone or in the form of a mixture.

As the polymerization initiator for the vinyl compound used in the present invention, a photopolymerization initiator and a thermal polymerization initiator are used. As the photopolymerization initiator, 2,2-dimethoxy-2-phenylacetophenone is used. , 1-hydroxycyclohexyl phenyl ketone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, Michler's ketone and the like can be mentioned as representative ones. The initiator is not limited, and these initiators may be used alone or in combination of two or more. Further, if necessary, a sensitizer such as an amine compound may be used in combination. As the thermal polymerization initiator, benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxide, azobisisobutyronitrile and the like are mentioned as typical ones. be able to. The amount of the polymerization initiator or thermal polymerization initiator used in the present invention is 0.1 to 10% by weight based on the vinyl compound.

[Epoxy compound] As a typical example of this, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexanecarboxylate, 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, a photoactive cation initiator such as triphenylsulfonium hexafluoroantimonate is used. In the liquid photocurable resin used in the present invention, if necessary, a leveling agent, a surfactant, an organic polymer compound, an organic plasticizer, and a filler such as organic or inorganic solid fine particles other than the above are blended. You may.

The liquid photo-curable resin used in the present invention may contain organic polymer solid fine particles and / or inorganic solid fine particles in any order, and may further contain other components as required. The mixing method of each component is not particularly limited. The light used in the optical three-dimensional modeling of the resin composition for optical three-dimensional modeling of the present invention may be ultraviolet light, visible light, infrared light, laser light or the like depending on the purpose. As a typical method of the optical three-dimensional modeling method used for the resin composition for optical three-dimensional modeling of the present invention, light is selectively applied to this composition which is liquid so that a cured layer having a desired pattern can be obtained. To form a cured layer, then supply an uncured liquid composition to the cured layer, and similarly irradiate light to newly form a cured layer continuous with the above-mentioned cured layer. This is a method of finally obtaining a desired three-dimensionally shaped object.

[0019]

Since the resin composition for stereolithography of the present invention uses solid fine particles and whiskers in combination, it is possible to prevent sedimentation of solid fine particles and maintain a preferable viscosity for molding and handling for a long time. The resin composition for use can be stably maintained. Furthermore, the optical three-dimensional molded article obtained from this composition not only has a small volume shrinkage and is excellent in dimensional accuracy, but also has a tensile strength, a tensile elastic modulus,
Flexural strength and flexural modulus are remarkably improved, and heat resistance is improved.

[0020]

[Examples] Next, more detailed description will be given with reference to Examples.
The present invention is not limited to these.

Synthesis Example (Synthesis of Urethane Acrylate Oligomer) After stirring, isophorone diisocyanate was trimerized into a 5-liter three-necked flask equipped with a cooling tube and a dropping funnel with a side tube.
1023 g of PDI terpolymer (manufactured by Sumitomo Bayer Co .; Dismodule Z-4372) and 0.076 g of dibutyltin laurate are charged, and the internal temperature is brought to 65 ° C. in an oil bath. 420.1 g of polyneopentylene adipate (manufactured by Asahi Denka Co., Ltd .; ADEKA NEWACE Y9-10) is charged into a dropping funnel with a side tube which is preliminarily kept at 50 ° C. The entire system is depressurized and the operation of returning to normal pressure with nitrogen gas is repeated to degas and replace nitrogen. The whole system is kept at normal pressure, and while maintaining the temperature of the flask contents in a nitrogen atmosphere at 65 ° C., the contents are stirred and the polyneopentylene adipate is added dropwise over 1 hour from the dropping funnel. After the dropping, the contents are kept at 65 ° C. for another hour and the reaction is continued with stirring. After cooling the temperature of the flask contents to 50 ° C., a dropping funnel was charged with a solution in which 254.5 g of 2-hydroxyethyl acrylate and 0.90 g of methylhydroquinone were homogeneously dissolved and mixed,
The contents of the flask are quickly added dropwise within a range where the temperature does not exceed 55 ° C., and the reaction is continued under stirring for 2 hours. The obtained urethane acrylate oligomer is taken out of the flask while the contents are warm. As a result of IR and elemental analysis, it was confirmed that the urethane acrylate oligomer obtained here had the following structural formula.

[0022]

Embedded image

Here, n has an average value of 4 and R represents the following groups.

[0024]

Embedded image

Example 1 (Preparation of Composition for Optical Modeling) 1320 g of urethane acrylate synthesized in Synthesis Example and polyethylene glycol 200 diacrylate (in a 5 liter three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel equipped with a side tube. 1080 g of Sartomer SR259) manufactured by Somar Corporation and 480 g of ethoxy-modified trimethylolpropane triacrylate (Sartomer SR454) manufactured by Somar Corporation were charged, and the contents were stirred and mixed for about 1 hour. In an environment where UV rays are cut,
120 g of 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Kaiggy; Irgacure 651) is added and mixed and stirred until completely dissolved. The obtained resin composition was treated with 14 g of Superdyne V201 (manufactured by Takemoto Yushi Co., Ltd.) as a leveling agent and glass beads 512 having an average particle size of 30 μm treated with an acrylic silane coupling agent.
Aluminum borate whiskers (diameter 0.5 μm to 0.7 μm, aspect ratio 50 to 7) treated with 0 g (40% by volume in the resin composition) and an acrylic silane coupling agent.
0) (Arborex YS-4; Shikoku Chemicals Co., Ltd.)
(Manufactured by Mitsui Chemicals Co., Ltd.), 1536 g (10% by volume) was added, and the mixture was stirred all day to degas. The viscosity of the obtained resin composition for stereolithography is 25.
It was 40,000 cps at ° C. A part of this resin composition for stereolithography was sampled in a test tube, and as a result of checking the stability of the resin, it was confirmed that a stable state was maintained for about 5 days and the composition did not separate. A predetermined dumbbell shape and a rectangle of 4.0 mm × 10.0 mm × 130 mm were obtained perpendicularly to the surface of the resin composition for stereolithography prepared by the focused Ar laser light (output: 500 mW, wavelength: 368 μm) as described above. It was irradiated so as to be received. After removing the resin liquid adhering to the obtained cured product by washing with isopropyl alcohol,
Post-cure was performed with 3 KW of ultraviolet light for 10 minutes. The tensile property and bending property of the obtained test piece were measured according to JIS standard 6911. The volumetric shrinkage was determined by measuring the liquid resin specific gravity and the molded product resin specific gravity. The results obtained are shown in Table 1 below.

Comparative Example 1 1320 g of urethane acrylate synthesized in Synthesis Example and polyethylene glycol 200 diacrylate (manufactured by Somar Co .; Sartomer SR259) were placed in a 5-liter three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel with a side tube.
080 g and ethoxy modified trimethylolpropane triacrylate (manufactured by Somar; Sartomer SR454)
Then, 480 g was charged, and the atmosphere was replaced with nitrogen under reduced pressure. 5 contents
The mixture was heated to 0 ° C. and mixed with stirring for about 1 hour. 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Kaiggy; Irgacure 651) in an environment cut by ultraviolet rays
Add 20 g and mix and stir until completely dissolved. The obtained resin composition for stereolithography has a temperature of 1550 cp at 25 ° C.
It was s. Test pieces were prepared from the resin composition obtained here in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table 1.

Example 2 The same as Example 1 except that 2253 g (40% by volume) of crosslinked polystyrene beads having an average particle size of 15 μm treated with an acrylic silane coupling agent were used in place of the glass beads used in Example 1. Then, a resin composition for stereolithography was prepared. The resin viscosity was 48,000 cps at 25 ° C. A test piece was prepared in the same manner as in Example 1, and the physical properties were measured in the same manner. The results are shown in Table 1.

Comparative Example 2 A stereolithographic resin composition was prepared in the same manner as in Example 1 except that the aluminum borate whiskers treated with an acrylic silane coupling agent were omitted from the stereolithographic resin composition described in Example 1. Prepared things. Test pieces were prepared in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table 1.

Example 3 In the same manner as in Example 1, except that the glass beads used in Example 1 were replaced with glass beads having an average particle size of 15 μm treated with an epoxysilane-based silane coupling agent. A resin composition was prepared. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 4 Instead of the glass beads used in Example 1, an average particle size of 15 μm was used.
A resin composition for stereolithography was prepared in the same manner as in Example 1 except that glass beads untreated with the silane coupling agent of m were used. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 5 The leveling agent used in Example 1, Superdyne V201 (manufactured by Takemura Yushi Co., Ltd.), was used in an amount of 7 g and an average particle size of 30 treated with an acrylic silane coupling agent.
The amount of the glass beads of μm used was changed to 714 g (10% by volume in the resin composition), and the mixture was mixed and degassed with stirring at room temperature for one day in the same manner as in Example 1. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 6 Instead of the crosslinked polystyrene beads having an average particle size of 15 μm used in Example 2, 2826 g of crosslinked polymethacrylate beads having an average particle size of 13 μm (50% by volume in the liquid photocurable resin composition) were used. A resin composition for stereolithography was prepared in the same manner as in Example 1 except for the above. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 7 2358 g of polyethylene beads having an average particle size of 30 μm (50% by volume in a liquid photocurable resin composition) instead of the crosslinked polystyrene beads having an average particle size of 15 μm used in Example 2
A resin composition for stereolithography was prepared in the same manner as in Example 1 except that was used. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 8 Instead of the polyethylene beads having an average particle size of 30 μm used in Example 7, polyethylene beads 23 having an average particle size of 6 μm were used.
A resin composition for stereolithography was prepared in the same manner as in Example 1 except that 58 g (50% by volume in the liquid photocurable resin composition) was used. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 9 In place of the polyethylene beads having an average particle size of 30 μm used in Example 8, 2358 g of polyethylene beads having an average particle size of 10 μm copolymerized with 6% by weight of acrylic acid (50 in the liquid photocurable resin composition) were used. A resin composition for stereolithography was prepared in the same manner as in Example 1 except that (% by volume) was used. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 10 The acrylic acid having the average particle size of 10 μm used in Example 9 was mixed with 6
Average particle size 1 treated with an acrylic silane-based silane coupling agent in place of polyethylene beads copolymerized by weight
A resin composition for stereolithography was prepared in the same manner as in Example 1 except that 2358 g of polyethylene beads (50% by volume in the liquid photocurable resin composition) obtained by copolymerizing 6% by weight of 0 μm acrylic acid was used. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 11 2826 g of a crosslinked polystyrene bead having an average particle diameter of 15 μm (liquid photocurable resin composition) treated with an acrylsilane silane coupling agent in place of the crosslinked polystyrene bead having an average particle diameter of 15 μm used in Example 2 50% by volume)
A resin composition for stereolithography was prepared in the same manner as in Example 1 except that was used. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation.

Example 12 2826 g of crosslinked polymethacrylate beads having an average particle size of 20 μm (liquid photo-curing) treated with an acrylsilane silane coupling agent instead of the crosslinked polymethacrylate beads having an average particle size of 13 μm used in Example 6 A resin composition for stereolithography was prepared in the same manner as in Example 1 except that 50% by volume in the resin composition was used. Since the whiskers were added, the obtained resin composition was stable for a long period of time without separation. Also, when basic magnesium sulfate, aluminum oxide, and silicon oxide were used as whiskers, the same excellent effect could be obtained.

Comparative Example 3 Superdyne V201 (manufactured by Takemoto Yushi Co., Ltd.) 1 was added to the resin composition for stereolithography obtained in Comparative Example 1 as a leveling agent.
Aluminum borate whiskers (diameter 0.5 μm to 0.7 μm) treated with 4 g and an acrylic silane coupling agent.
m, aspect ratio 50-70) (Arborex YS-
4: 1360 g (15% by volume in the resin composition) of Shikoku Kasei Co., Ltd. was added, and the mixture was degassed with stirring at room temperature for one day. The viscosity of the obtained resin composition for stereolithography is 10 at 25 ° C.,
It was 600 cps. Test pieces were prepared from the resin composition obtained here in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table 1.

[0040]

[Table 1]

As is apparent from Table 1, the volumetric shrinkage of the molded articles of the examples of the present invention was much smaller than that of Comparative Example 1, and the volumetric shrinkage was significantly improved. I understand. Further, the tensile elastic modulus and the bending elastic modulus are remarkably improved. On the other hand, in Comparative Examples 1 to 3, it can be seen that the volumetric shrinkage is large and the dimensional accuracy is not good. Further, in Comparative Example 3, the physical properties are excellent, but it can be seen that the volumetric shrinkage is large and the dimensional accuracy is not good, but in Example 1 of the present invention, the volumetric shrinkage is much smaller.

[0042]

INDUSTRIAL APPLICABILITY In the present invention, since the liquid photo-curable resin is used in combination with solid fine particles and whiskers, the volumetric shrinkage is small and other physical properties are also excellent, so that the stereolithography is excellent in practicality. The thing is obtained.

Claims (12)

[Claims] 1. A resin composition for optical three-dimensional modeling, characterized in that a liquid photocurable resin contains solid fine particles and whiskers. 2. The proportion of solid fine particles and whiskers is 14
The resin composition for optical three-dimensional modeling according to claim 1, wherein the resin composition is in the range of from 1: 6 to 1. 3. The solid fine particles have an average particle size of 3 to 70 μm, and the whiskers have a diameter of 0.3 μm to 1 μm and a length of 10.
The resin composition for optical three-dimensional modeling according to claim 1 or 2, wherein the resin composition is composed of µm to 70 µm and an aspect ratio of 10 to 100. 4. The resin composition for optical three-dimensional modeling according to claim 1, wherein the solid fine particles are inorganic solid fine particles and organic polymer solid fine particles. 5. The optical three-dimensional modeling according to any one of claims 1 to 4, wherein the ratio of the inorganic solid fine particles and the organic polymer solid fine particles is 1: 9 to 9: 1. Resin composition. 6. The optical solid modeling according to claim 1, wherein the inorganic solid fine particles are at least one selected from glass beads, talc fine particles, and silicon oxide fine particles. Resin composition. 7. The organic polymer solid fine particles are at least one selected from a crosslinked polystyrene polymer, a crosslinked polymethacrylate polymer, a polyethylene polymer, and a polypropylene polymer. A resin composition for optical three-dimensional modeling according to any one of claims 1 to 6. 8. The whisker comprises at least one of an aluminum borate-based compound, a basic magnesium sulfate-based compound, aluminum oxide and a silicon oxide-based compound. Which is a resin composition for optical three-dimensional modeling. 9. The method according to claim 1, wherein the solid fine particles are treated with at least one silane coupling agent selected from aminosilane, epoxysilane and acrylsilane. A resin composition for optical three-dimensional modeling. 10. The liquid photocurable resin is mainly composed of an ethylenically unsaturated compound, and the solid fine particles are treated with an acrylsilane silane coupling agent. The resin composition for optical three-dimensional modeling according to claim 9. 11. The liquid photo-curable resin is mainly composed of an epoxy compound, and the solid fine particles are treated with an epoxysilane-based silane coupling agent. 10. The resin composition for optical three-dimensional modeling according to any one of 10. 12. The organic polymer solid fine particles are polyethylene solid fine particles obtained by copolymerizing 1 to 10% by weight of an acrylic acid-based compound.
The resin composition for optical three-dimensional modeling according to any one of 1.