JP2762389B2 - Optical three-dimensional molding resin composition - Google Patents

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 in particular, has excellent volumetric shrinkage before and after curing, excellent dimensional accuracy, and 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 Patent Application Laid-Open No. Sho 56-144478 discloses a method of supplying a three-dimensional object by supplying a required amount of light energy to a photocurable resin. No. 247515 proposed a basic practical method. Thereafter, a similar or improved technique has been disclosed in JP-A-62-35966 and JP-A-1-20491.
5, JP-A-2-113925, JP-A-2-113925
145616, JP-A-2-153722,
It is disclosed in JP-A-3-15520, JP-A-3-21432, JP-A-3-41126 and the like.

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

Conventionally, photocurable resins used in the optical three-dimensional molding method include modified polyurethane (meth) acrylate, oligoester acrylate, urethane acrylate, epoxy acrylate, photosensitive polyimide, aminoalkyd, and the like. And recently,
-204915, JP-A-1-213304, JP-A-2-28261, JP-A-2-7561
7, JP-A-2-145616, JP-A-3-
Various improved techniques are disclosed in JP-A-104626, JP-A-3-114732 and JP-A-3-114733.

[0004]

In the optical three-dimensional molding method, the photocurable resin used is easy to handle.
From the viewpoint of modeling speed, modeling accuracy, etc., the resin viscosity is relatively low, from the viewpoint of dimensional accuracy of the molded product, the volume shrinkage ratio during curing is low, and the mechanical properties of the obtained molded product are sufficiently high. Not only are they required, but recently, high heat resistance is required depending on the application. However,
None of the conventional liquid photocurable resins described above has necessarily been satisfactory in terms of these characteristics and particularly dimensional accuracy.

Therefore, the present inventor has continued his intensive research on the improvement of the above-mentioned various properties. As a result, when certain organic polymer solid fine particles and / or inorganic solid fine particles were blended into a liquid photo-curable resin, the mechanical The inventors have found that not only the rigidity is remarkably improved but also the volume shrinkage is much lower than expected, and applied for a patent here.As a result of further research, when whiskers were added to the solid fine particles, a long time was obtained. The present inventors have found that not only a stable liquid material can be obtained without sedimentation of solid fine particles, but also a material having more excellent mechanical rigidity and volumetric shrinkage can be obtained, and the present invention has been accomplished. Therefore, an object of the present invention is to have a favorable viscosity in molding handling, and to be a long-term stable optical three-dimensional molding resin composition, to have sufficiently high mechanical properties, and to be excellent in heat resistance. Another object of the present invention is to provide an optical three-dimensionally molded resin composition which has a small volumetric shrinkage ratio and therefore provides a three-dimensionally shaped object having excellent dimensional accuracy.

[0006]

The above objects of the present invention are attained 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 according to the above item 1, wherein the resin composition is 1 to 1. (3) The solid fine particles have an average particle diameter 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 μm.
3. The resin composition for optical three-dimensional modeling according to any one of the above items 1 or 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 (1) to (3) above, wherein the solid fine particles are inorganic solid fine particles and organic polymer solid fine particles. (5) The resin according to any one of (1) to (4) above, wherein the ratio of the inorganic solid fine particles to the organic high molecular solid fine particles is 1: 9 to 9: 1. Composition. (6) The inorganic solid fine particles are glass beads, talc fine particles,
Item 6. 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 above-mentioned item 1, wherein 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. To the sixth
Item 14. The resin composition for optical three-dimensional modeling described in any one of Items above. (8) The whisker according to any one of (1) to (7), wherein the whisker comprises at least one of an aluminum borate compound, a basic magnesium sulfate compound, aluminum oxide, and a silicon oxide compound. An optical stereolithography resin composition. (9) The optical device as described in any one of (1) to (8) above, wherein the solid fine particles are treated with at least one or more silane coupling agents of aminosilane, epoxysilane, and acrylsilane. Resin composition for three-dimensional modeling. (10) The liquid crystal display device according to any one of the above items 1 to 3, wherein the liquid photocurable resin is mainly composed of an ethylenically unsaturated compound, and the solid fine particles are treated with an acrylic silane-based silane coupling agent. Item 10. The resin composition for optical three-dimensional modeling according to any one of Items 9 to 10. (11) The above-mentioned items 1 to 10, wherein the liquid photocurable resin is mainly composed of an epoxy-based 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 the above. (12) The optical element according to any one of (1) to (11) above, 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.

Hereinafter, the present invention will be described in more detail. The stereolithography resin composition of the present invention, having the above-described constitution, has a preferable viscosity for molding and handling and has a stable liquid stereolithography for a long time. Therefore, the optical three-dimensional structure obtained from this composition has a small volume shrinkage, excellent dimensional accuracy, and has sufficiently high mechanical properties and heat resistance. Furthermore, the resin composition for stereolithography of the present invention, in which the whisker is contained, the optical three-dimensional molded article obtained therefrom has not only an excellent dimensional accuracy but also a tensile strength,
The tensile modulus, flexural strength and flexural modulus have been significantly improved,
And the heat resistance is improved.

[0008] The resin composition for stereolithography used in the present invention has a favorable viscosity for molding handling by containing mixed particles of solid fine particles and whiskers and is stable for liquid stereolithography for a long time. The resin composition can be retained, and in addition, a three-dimensional structure with excellent mechanical rigidity and heat resistance and a volume shrinkage much smaller than expected can be obtained, and thus dimensional accuracy can be further improved. Can be This makes it possible to develop a wide range of new uses of optical three-dimensional objects in the present invention. Here, in “having organic polymer solid fine particles and / or inorganic solid fine particles”, “and / or” refers to the case where organic polymer solid fine particles and inorganic solid fine particles have together and the organic polymer solid fine particles and inorganic solid fine particles. Of these, it is used to mean both aspects of the case where either one has only one.

The organic polymer solid fine particles and / or inorganic solid fine particles used in the present invention each have an average particle diameter of 3 to 3.
70 μm, preferably 10 to 60 μm, and more preferably 15 to 50 μm. In this case, the particle diameters of the organic polymer solid fine particles and the inorganic solid fine particles may be the same or different, and preferably have the same particle diameter. When the average particle diameter of these solid fine particles is smaller than 3 μm, the viscosity of the resin is unnecessarily increased, so that the resin cannot be blended in a desired ratio. At this time, scattering of active energy occurs, and the accuracy of the formed object is reduced. The whiskers used in the present invention have a diameter (or width) of 0.3 μm to 1 μm, preferably 0.3 μm to 0.7 μm, and a length of 1 μm.
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 whisker used in the present invention is smaller than 10, the effect of the present invention when the whisker is added, that is, a particular improvement in mechanical strength and a decrease in volume shrinkage cannot be obtained. It is not preferable because the viscosity of the resin simply increases unnecessarily. On the other hand, if the aspect ratio of the whisker increases, the effect of improving the mechanical strength and decreasing the volume shrinkage is expected, but if the aspect ratio becomes too large as 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 lateral accuracy of the formed object. Therefore, the size of the aspect ratio is limited, and the aspect ratio is preferably 100 or less, more preferably 70 or less. In the present invention, the mixing ratio between the solid fine particles and the whiskers is 14 to 1: 6 to 1, preferably 12 to 1: 5 to 1. If it is outside this range, a very favorable result 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.
Preferably it is 10 to 55% by volume. The compounding ratio of these organic polymer solid fine particles and or inorganic solid fine particles,
When the amount is less than 5% by volume, the effect of the present invention is not sufficiently exhibited. On the other hand, when the compounding ratio is more than 70% by volume, the viscosity of the optical three-dimensional modeling resin composition becomes too high. As a result, the mechanical strength of the obtained molded article is lowered, which is not only unfavorable but also involves difficulty in the shaping operation, which is not preferable.

The viscosity of the resin composition for stereolithography of the present invention is preferably from 5,000 cps to 10 when organic fine solid particles and / or inorganic solid fine particles are used.
000 cps is a guide. In the case of using a whisker, the viscosity of the resin composition for optical three-dimensional modeling of the present invention may be lower than that in the case of using the solid fine particles, and the viscosity is preferably 1,000 cps or more. In the present invention, the ratio of the organic polymer solid fine particles to the inorganic solid fine particles is 9: 1 when these are mixed.
It can be adjusted arbitrarily in the range of １ ： 1: 9. Preferably it is 8: 2 to 2: 8. The mixing ratio of the whisker to the liquid photocurable resin used in the present invention is 5 to 30.
%, Preferably 7 to 20% by volume. When the mixing ratio of the whisker is less than 5% by volume, the effect of the present invention is not sufficiently exhibited, while the mixing ratio is
If it exceeds 30% by volume, the viscosity of the resin composition for optical three-dimensional modeling becomes too high, which causes not only difficulty in use but also impairment of light permeation, and there is a problem in the modeling operation, so that it cannot be used. .

As preferred organic polymer solid fine particles used in the present invention, preferred are cross-linked polystyrene-based polymers, cross-linked polymethacrylate-based polymers, polyethylene-based polymers, polypropylene-based polymers, and the like. As the inorganic solid fine particles used in the present invention,
Typical examples thereof include glass beads, talc fine particles, and silicon oxide fine particles, but examples of the organic polymer solid fine particles and the inorganic solid fine particles are not limited thereto, and many other types are used. The whiskers used in the present invention comprise at least one of aluminum borate-based compounds, magnesium hydroxide-based compounds, aluminum oxide and silicon oxide-based compounds, and are preferably aluminum borate-based compounds and magnesium hydroxide-based compounds. Compound or aluminum oxide-based compound. In the present invention, it is preferable to contain a whisker 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 those treated with a silane coupling agent, and the organic polymer solid fine particles treated with such a silane coupling agent are preferably used. And when inorganic 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, epoxy silane, acrylic silane and the like are preferably used. The effect of the type of the silane coupling agent differs depending on the liquid photocurable resin used. When a vinyl-based unsaturated compound is used as the liquid photocurable resin, an acrylsilane-based silane coupling agent is most preferable.When an epoxy-based compound is used as the liquid photocurable resin, an epoxysilane-based silane coupling agent is used. It is most effective to use.
Further, when a polyethylene-based polymer, a polypropylene-based polymer, or the like is used as the organic polymer solid fine particles, these solid fine particles are mixed with at least 1 to 10% by weight, preferably 5 to 8% by weight of an acrylic acid compound. The use of a polymerized product can provide more favorable results. When the amount of the acrylic acid compound is less than 1% by weight, there is almost no effect of the mechanical strength exhibited by the treatment with the silane coupling agent, and the amount of the acrylic acid compound is 10% by weight.
Beyond, the effect does not change much. The liquid photocurable resin used in the present invention may be any of a polymerizable vinyl compound, an epoxy compound, etc., a monofunctional compound,
Any monomer and / or oligomer of the polyfunctional compound may be used. These monofunctional compounds and polyfunctional compounds are not particularly limited, and typical examples of the liquid photocurable resin are given below.

[Polymerizable vinyl compound] 1) Monofunctional compounds include isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, -Hydroxypropyl acrylate, propylene glycol monoacrylate, vinyl pyrrolidone, acrylamide, vinyl acetate, styrene and the like.

2) Examples of the polyfunctional compound include trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, and tetraethylene glycol diacrylate. , Polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-
Examples include hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate, diallyl phthalate, and the like. One or more of such monofunctional compounds and / or polyfunctional compounds can be used alone or in the form of a mixture.

As the polymerization initiator of 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-hydroxycyclohexylphenyl ketone, acetophenone, benzophenone, xanthone, fluorenone, bezaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, Michler's ketone, and the like. The initiator is not limited, and these initiators can be used alone or in combination of two or more. If necessary, a sensitizer such as an amine compound can be used in combination. Typical examples of the thermal polymerization initiator include benzoyl peroxide, t-butylperoxybenzoate, dicumyl peroxide, diisopropylperoxydicarbonate, t-butylperoxide, azobisisobutyronitrile, and the like. be able to. The amount of the polymerization initiator or the thermal polymerization initiator used in the present invention is 0.1 to 10% by weight based on the vinyl compound.

[Epoxy compounds] Typical examples thereof include 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 other fillers such as organic or inorganic solid fine particles other than the above are blended. May be.

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. Other components may be added as needed. The mixing method of each component is not particularly limited. The light used for optically three-dimensionally molding 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 optical three-dimensional modeling resin composition of the present invention, light is selectively applied so that a cured layer having a desired pattern is obtained in a liquid composition. To form a cured layer, and then supply the uncured liquid composition to the cured layer, and repeat the laminating operation of similarly irradiating light to newly form a cured layer continuous with the cured layer. Is a method of finally obtaining a target three-dimensional object.

[0019]

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

The mixing ratio in the present specification indicates a volume ratio unless otherwise specified.

The present invention will be described in more detail with reference to the following examples.
The present invention is not limited to these.

Synthesis Example (Synthesis of Urethane Acrylate Oligomer) After stirring, isophorone diisocyanate was trimerized in a 5-liter three-necked flask equipped with a cooling tube and a dropping funnel with side tubes.
1023 g of PDI terpolymer (manufactured by Sumitomo Bayer; Dismodule Z-4372) and 0.076 g of dibutyltin laurate are charged, and the internal temperature is adjusted to 65 ° C. in an oil bath. 420.1 g of polyneopentylene adipate (Adeka New Ace Y9-10; manufactured by Asahi Denka Co., Ltd.) is charged into a dropping funnel with a side tube which is kept at 50 ° C. in advance. The operation of reducing the pressure in the entire system and returning to normal pressure with nitrogen gas is repeated to perform degassing and nitrogen replacement. The entire system is brought to normal pressure, and polyneopentyl adipate is added dropwise from a dropping funnel over 1 hour while stirring the contents in a nitrogen atmosphere while maintaining the contents of the flask at 65 ° C. After the addition, the content is maintained at 65 ° C. for another hour, and the reaction is continued with stirring. After cooling the temperature of the contents of the flask to 50 ° C., a liquid obtained by uniformly dissolving and mixing 0.90 g of methylhydroquinone in 254.5 g of 2-hydroxyethyl acrylate was added to the dropping funnel.
The temperature of the contents in the flask is dropped rapidly within a range not exceeding 55 ° C., and then the reaction is continued with stirring for 2 hours. The resulting 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 obtained urethane acrylate oligomer 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 shaping) In a 5-liter three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel equipped with a side tube, 1320 g of urethane acrylate synthesized in the synthesis example and polyethylene glycol 200 diacrylate ( 1080 g of Sartomer SR259 (manufactured by Somar) and 480 g of ethoxy-modified trimethylolpropane triacrylate (Sartomer SR454 manufactured by Somar) were charged and the contents were stirred and mixed for about 1 hour. Under the environment that cut ultraviolet rays,
120 g of 2,2-dimethoxy-2-phenylacetophenone (Circa Kaigie; Irgacure 651) is added, and mixed and stirred until completely dissolved. The resulting 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 whisker treated with 0 g (40% by volume in the resin composition) and an acrylic silane coupling agent (diameter 0.5 μm to 0.7 μm, aspect ratio 50 to 7)
0) (Arbolex YS-4; Shikoku Chemical Industry Co., Ltd.)
1536 g (10% by volume) was added, and the mixture was stirred and defoamed all day. The viscosity of the resin composition for stereolithography obtained is 25.
It was 40,000 cps at ° C. A part of the resin composition for stereolithography was collected in a test tube, and as a result of examining 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 converging the focused Ar laser beam (output 500 mW, wavelength 368 μm) as described above. Irradiation. After washing and removing the resin liquid attached to the obtained cured product with isopropyl alcohol,
Post cure was performed for 10 minutes with 3 KW ultraviolet light. The tensile properties and bending properties of the obtained test pieces were measured in accordance with JIS standard 6911. The volume shrinkage was determined by measuring the specific gravity of the liquid resin and the specific gravity of the molded resin. Hereinafter, the obtained results are shown in Table 1.

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

Example 2 In the same manner as in 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 was used instead of the glass beads used in Example 1. To prepare a stereolithographic resin composition. 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 resin composition for stereolithography was prepared in the same manner as in Example 1 except that the aluminum borate whisker treated with the acrylic silane coupling agent was omitted from the resin composition for stereolithography described in Example 1. I mixed 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 The same procedure as in Example 1 was repeated except that glass beads having an average particle diameter of 15 μm treated with an epoxysilane-based silane coupling agent were used instead of the glass beads used in Example 1. A resin composition was prepared. Since the whiskers were added, the resulting resin composition was stable for a long time without separation.

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

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

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

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

Example 8 Polyethylene beads 23 having an average particle diameter of 6 μm were used in place of the polyethylene beads having an average particle diameter of 30 μm used in Example 7.
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 resulting resin composition was stable for a long time without separation.

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

Example 10 The acrylic acid having an average particle diameter of 10 μm used in Example 9
Average particle size 1 treated with an acrylic silane-based silane coupling agent instead 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 μ% by weight of acrylic acid of 0 μm was used. Since the whiskers were added, the resulting resin composition was stable for a long time without separation.

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

Example 12 Instead of the crosslinked polymethacrylate beads having an average particle diameter of 13 μm used in Example 6, 2826 g of crosslinked polymethacrylate beads having an average particle diameter of 20 μm treated with an acrylsilane silane coupling agent (liquid photocuring) Except for using 50% by volume of the conductive resin composition), to prepare a resin composition for stereolithography in the same manner as in Example 1. Since the whiskers were added, the resulting resin composition was stable for a long time without separation. Similarly, when basic magnesium sulfate, aluminum oxide, and silicon oxide were used as whiskers, excellent effects could be obtained.

Comparative Example 3 Superdyne V201 (manufactured by Takemoto Yushi Co., Ltd.) was used as a leveling agent in the stereolithographic resin composition obtained in Comparative Example 1.
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) (Albolex YS-
4: 1360 g (15% by volume in the resin composition) of Shikoku Chemical Industry Co., Ltd.) was added, followed by stirring and defoaming at room temperature for one day. The viscosity of the obtained resin composition for stereolithography was 10, at 25 ° C.
It was 600 cps. Test pieces were prepared from the resin composition obtained 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 clear from Table 1, the volume shrinkage of the molded article of the example of the present invention was much smaller than that of Comparative Example 1, and the volume shrinkage was greatly improved. I understand. Further, the tensile modulus and the flexural modulus are remarkably improved. On the other hand, in Comparative Examples 1 to 3, it can be seen that the volume shrinkage is large and the dimensional accuracy is not good. Further, although each physical property is excellent in Comparative Example 3, it is understood that the volume shrinkage is large and the dimensional accuracy is not good, but in Example 1 of the present invention, the volume shrinkage is much smaller.

[0042]

According to the present invention, since the liquid photocurable resin is used in combination with the solid fine particles and the whiskers, the volume shrinkage is small and other physical properties are also excellent. Things are obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 7/16 C08K 7/16 C08L 101/00 C08L 101/00 G03F 7/027 G03F 7/027

Claims (6)

(57) [Claims] An optical three-dimensional molding resin composition comprising a liquid photocurable resin containing solid fine particles and whiskers having a ratio of solid fine particles to whiskers of 14: 1 to 6: 1. 2. The liquid photocurable resin has an average particle size of 3 to 70 μm.
m solid fine particles and a diameter of 0.3 μm to 1 μm,) a length of 10
A resin composition for optical three-dimensional modeling, characterized by containing whiskers having a thickness of from 70 to 70 [mu] m and an aspect ratio of from 10 to 100. 3. The resin composition for optical shaping according to claim 1, wherein the solid fine particles are inorganic solid fine particles and / or organic polymer solid fine particles. 4. The optical solid according to claim 1, wherein the solid fine particles contain at least one kind of inorganic solid fine particles selected from glass beads, talc fine particles, and silicon oxide fine particles. A molding resin composition. 5. The whisker according to claim 1, wherein the whisker is at least one of an aluminum borate compound, a basic magnesium sulfate compound, an aluminum oxide polymer and a silicon oxide compound. The resin composition for optical three-dimensional modeling according to the above. 6. The optical solid according to claim 1, wherein the solid fine particles have been treated with at least one or more silane coupling agents of aminosilane, epoxysilane, and acrylsilane. A molding resin composition.