JP2554443B2 - Resin composition for optical three-dimensional modeling - 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 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.

[0002]

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 a 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.

[0005]

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 photo-curable resins have been provided that are satisfactory in various characteristics and especially in dimensional accuracy. Therefore,
The present inventor, as a result of earnestly continuing to improve the above-mentioned various properties, when a predetermined whisker was added to a liquid photocurable resin, not only the mechanical strength was significantly improved but also the volume shrinkage ratio was expected. Finds that it will fall far beyond,
The present invention is completed here.

Therefore, an object of the present invention is to provide a three-dimensional object which has a preferable viscosity in terms of modeling and handling, has sufficiently high mechanical properties, is excellent in heat resistance and has a small volume shrinkage ratio, and is therefore excellent in dimensional accuracy. It is to provide a resin composition for optical three-dimensional modeling that can be provided.

[0008]

The above objects of the present invention can be achieved by the following inventions. (1) An optical three-dimensional modeling resin composition comprising a liquid photocurable resin and 5 to 30% by volume of whiskers having a diameter of 0.3 μm to 1 μm, a length of 10 μm to 70 μm, and an aspect ratio of 10 to 100.

(2) The whiskers are composed of at least one of aluminum borate compounds, magnesium hydroxide sulfate compounds, aluminum oxide, titanium oxide compounds and silicon oxide compounds.
The resin composition for optical three-dimensional modeling according to item 1.

(3) The optical according to any one of (1) and (2) above, wherein the whiskers are treated with at least one silane coupling agent selected from aminosilane, epoxysilane and acrylsilane. Resin composition for stereoscopic modeling.

(4) The liquid photocurable resin is mainly composed of an ethylenically unsaturated compound, and the whiskers are treated with an acrylsilane silane coupling agent. ) To (2), the resin composition for optical three-dimensional modeling according to any one of (1) to (2).

(5) The liquid photocurable resin is mainly composed of an epoxy unsaturated compound, and the whiskers are treated with an epoxysilane silane coupling agent. ) To (2), the resin composition for optical three-dimensional modeling according to any one of (1) to (2).

The present invention will be described in more detail below. The optical three-dimensional modeling resin composition used in the present invention has a mechanical rigidity and a heat resistance excellent by having a whisker, and at the same time, a volume shrinkage ratio that is much smaller than expected can be obtained, and therefore the dimensional accuracy is high. A more excellent three-dimensional object can be obtained. In the present invention, this enables development of a wide range of new uses for optical three-dimensionally shaped objects.

The whisker used in the present invention comprises at least one selected from the group consisting of aluminum borate compounds, magnesium hydroxide sulfate compounds, aluminum oxide, titanium oxide compounds and silicon oxide compounds, preferably aluminum borate. System compounds, magnesium hydroxide sulfate-based compounds, aluminum oxide and titanium oxide-based compounds.

The whiskers used in the present invention have a diameter (or width) of 0.3 μm to 1 μm, preferably 0.1.
3 μm to 0.7 μm, and the length is 10 μm to 70 μm.
μm, and preferably in the range of 20 μm to 50 μm. 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 viscosity of the resin becomes too high. Not only the fluid elasticity becomes high and the shaping operation becomes difficult, but at the same time, the length of the whiskers becomes long and the side accuracy of the shaped article decreases, so 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.

The blending ratio of the whiskers used in the present invention to the liquid photocurable resin is 5 to 30% by volume,
It is preferably 7 to 20% by volume. If the blending ratio of the whiskers is less than 5% by volume, the effect of the present invention is not sufficiently exhibited, while if the blending ratio exceeds 30% by volume, the viscosity of the resin composition for optical three-dimensional modeling is low. Is too high, which not only causes difficulty in use but also impedes the penetration of light, which causes problems in the molding operation and cannot be used.

The viscosity of the resin composition for optical three-dimensional modeling of the present invention is preferably 1,000 cps to 100,000 cps.
The standard is ps. The whiskers used in the present invention are
It is preferable to use those treated with a silane coupling agent such as aminosilane, epoxysilane, and acrylic silane. When using a whisker treated with such a silane coupling agent, a particularly preferable one having excellent mechanical strength is used. Is obtained.

The effect of the type of the silane coupling agent varies depending on the liquid photocurable resin used. For example, when a vinyl unsaturated compound is used as the liquid photocurable resin, the acrylic silane silane coupling agent is most preferable. When an epoxy compound is used as the liquid photocurable resin, it is most effective to use an epoxysilane silane coupling agent.

The liquid photocurable resin used in the present invention may contain organic polymer solid fine particles and / or inorganic solid fine particles, and as the organic polymer solid fine particles,
Crosslinked polystyrene-based polymers, crosslinked polymethacrylate-based polymers, polyethylene-based polymers, polypropylene-based polymers and the like are mentioned as representatives of preferable ones, and as inorganic solid fine particles, glass beads, talc fine particles,
Typical examples thereof include fine particles of silicon oxide.
Examples of the organic polymer solid fine particles and the inorganic solid fine particles are not limited to these, and many others are used.

The organic polymer solid fine particles and / or the inorganic solid fine particles are preferably treated with a silane coupling agent similar to the one used for the treatment of the whiskers, which is a special machine for three-dimensional molded objects like the whiskers. It is possible to obtain a preferable one having excellent dynamic strength.

The liquid photocurable resin used in the present invention is
Any of a polymerizable vinyl compound and an epoxy compound may be used, and a monomer and / or oligomer of a monofunctional compound or a polyfunctional compound is 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, zinc pentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2- Examples thereof include hydroxypropyl acrylate, propylene glycol acrylate, vinylpyrrolidone, acrylamide, vinyl acetate, styrene and the like.

2) 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 such monofunctional compounds and / or polyfunctional compounds may 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, and the photopolymerization initiator is 2,2-dimethoxy-2-phenylacetophenone. , 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 typical. It can be mentioned as a thing. The amount of the polymerization initiator or the thermal polymerization initiator used in the present invention is 0.1 to 0.1 with respect to the vinyl compound.
It is 10% by weight.

[Epoxy compound] As typical examples 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, an energy active 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, a filler other than the above, such as organic beads, and other than the above. Inorganic fillers such as glass beads may be added. As the resin composition of the present invention, the vinyl-based compound and the epoxy-based compound may be used alone or in combination with each other, and other components may be blended as necessary. The mixing method 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 molding method used for the resin composition for optical three-dimensional molding of the present invention, liquid composition is used so that a cured layer having a desired pattern can be obtained. Is selectively irradiated to form a cured layer,
Then, an uncured liquid composition is supplied to the cured layer, and similarly, light irradiation is performed to newly form a cured layer continuous with the above-mentioned cured layer. It is a way to get things.

[0031]

[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 has been 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. Make the whole system normal pressure,
While maintaining the temperature of the contents of the flask at 65 ° C. in a nitrogen atmosphere, polyneopenthylene adipate is added dropwise from the dropping funnel over one hour while stirring the contents. 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., 2-hydroxyethyl acrylate 2 was added to the dropping funnel.
A liquid in which 0.90 g of methylhydroquinone was homogeneously dissolved and mixed in 54.5 g was charged, and the temperature of the flask contents was 55 ° C.
Quickly drop in a range not exceeding the value, and then with stirring for 2 hours,
Continue the reaction. 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 obtained urethane acrylate oligomer had the following structural formula.

[0034]

Embedded image

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

[0036]

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 with a side tube) 1080 g of Sartomer SR259) manufactured by Somar Co. and 480 g of ethoxy-modified trimethylolpropane triacrylate (Sartomer SR454 manufactured by Somar Co.) were charged and degassed with nitrogen under reduced pressure. The contents were heated to 50 ° C. and mixed with stirring for about 1 hour.

120 g of 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Kaiggy; Irgacure 651) is added in an environment where ultraviolet rays are cut, and mixed and stirred until completely dissolved. Superdyne V201 (Takemura Yushi Co., Ltd.) is used as a leveling agent in the obtained resin composition.
14 g) and aluminum borate whiskers (diameter 0.5 μm to 0.1 μm) treated with an acrylic silane coupling agent.
7 μm, aspect ratio 50-70) (Arborex Y
S-4: 1360 g (15% by volume in the resin composition) of Shikoku Chemicals 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 1 at 25 ° C.
It was 0,600 cps.

Focused Ar laser light (output 500 m
W and a wavelength of 368 μm) were irradiated perpendicularly to the surface of the resin composition for stereolithography prepared as described above so that a predetermined dumbbell shape and a rectangle of 4.0 mm × 10.0 mm × 130 mm were obtained. After removing the resin liquid adhering to the obtained cured product by washing with isopropyl alcohol, post-curing was performed with 3 KW of ultraviolet light for 10 minutes. The obtained test piece was measured for tensile properties and bending properties according to JIS standard 6911, and for heat distortion temperature according to JIS standard K7207. Further, 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; 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.

120 g of 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Kaiggy; Irgacure 651) is added in an environment where ultraviolet rays are cut, and mixed and stirred until completely dissolved. The obtained resin composition for stereolithography was 1550 cps at 25 ° C. 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 Alborex YS-1 (manufactured by Shikoku Chemicals Co., Ltd.), which is an aluminum borate whisker treated with an aminosilane-based silane coupling agent in place of Arborex YS-4 used in Example 1, was used. A resin composition for stereolithography was prepared in the same manner as in Example 1. Test pieces were 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.
It was shown to.

Example 3 Alborex Y (Shikoku Chemical Industry Co., Ltd.), which is an aluminum borate whisker which is not treated with a coupling agent in place of Arborex YS-4 used in Example 1, is used.
A resin composition for stereolithography was prepared in the same manner as in Example 1 except that the resin composition was used. A test piece was prepared in the same manner as in Example 1, the physical properties were measured in the same manner, and the results are shown in Table 1.

Comparative Example 2 For stereolithography in the same manner as in Example 1 except that the amount of the aluminum borate whiskers Arborex YS-4 added was changed to 320 g (4% by volume in the composition). A resin composition was prepared. The resin viscosity was 2300 cps at 25 ° C. A test piece was prepared in the same manner as in Example 1, the physical properties were measured in the same manner, and the results are shown in Table 1.

Comparative Example 3 A resin for stereolithography was prepared in the same manner as in Example 1 except that the amount of Alborex YS-4, which is an aluminum borate whisker, was changed to 4150 g (35% by volume in the composition). Attempts were made to formulate the composition. The resin viscosity was 43000 cps at 25 ° C. However, a test piece was prepared from this resin composition in the same manner as in Example 1, but the curing depth was not sufficient and delamination was observed, and a test piece for measuring physical properties could not be obtained.

Comparative Example 4 In the same manner as in Example 1, 1133 g (15% by volume in the composition) of a silicon oxide whisker having an aspect ratio of 3 was used instead of the aluminum borate whisker Arborex YS-4. Then, a resin composition for stereolithography was prepared. The viscosity of the resin composition is 6500 at 25 ° C.
It was cps. Test pieces were prepared in the same manner as in Example 1, the physical properties were measured, and the results are shown in Table 1.

Comparative Example 5 In Comparative Example 4, a resin liquid was prepared using a silicon oxide compound having an aspect ratio of 150. Using this resin solution, a test piece was produced in the same manner as in Example 1, but a whisker-like substance was generated on many side faces, and a preferable shaped product could not be obtained.

[0048]

[Table 1]

As is clear from Table 1, the molded articles of the examples of the present invention have markedly improved tensile strength, tensile elastic modulus, and heat resistance, and the volumetric shrinkage is smaller than that of Comparative Example 1. It can be seen that the volume shrinkage ratio is improved. In Comparative Examples 1 and 2, it can be seen that the volumetric shrinkage is large and the dimensional accuracy is not good, and other physical properties are not changed. Further, in Comparative Example 4, the physical properties other than the present invention having an aspect ratio of 3 are inferior to the physical properties of the present invention.

[0050]

Since the resin composition for stereolithography of the present invention contains whiskers, the optical three-dimensional molded article obtained from this has remarkable tensile strength, tensile elastic modulus, bending strength and bending elastic modulus. And the heat resistance is improved. Further, this optical three-dimensional model has a small volume contraction rate, and therefore, one having excellent dimensional accuracy can be obtained.

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Claims (5)

(57) [Claims] 1. The liquid photocurable resin has a diameter of 0.3 μm to 1 μm.
m, length 10 μm to 70 μm, aspect ratio 10 to 10
A resin composition for optical three-dimensional modeling, which comprises 5 to 30% by volume of 0 whiskers. 2. The whisker comprises at least one of an aluminum borate compound, a magnesium hydroxide sulfate compound, aluminum oxide, a titanium oxide compound and a silicon oxide compound. A resin composition for optical three-dimensional modeling. 3. The optical three-dimensional modeling according to claim 1, wherein the whiskers are treated with at least one silane coupling agent selected from aminosilane, epoxysilane and acrylsilane. Resin composition. 4. The liquid photocurable resin is mainly composed of an ethylenically unsaturated compound, and the whiskers are treated with an acrylsilane silane coupling agent. 2. The resin composition for optical three-dimensional modeling according to any one of 2. 5. The liquid photocurable resin mainly comprises an epoxy unsaturated compound, and the whiskers are treated with an epoxysilane silane coupling agent. 2. The resin composition for optical three-dimensional modeling according to any one of 2.