KR100266140B1 - Resin composition for production of a three-dimensional obje - Google Patents

Abstract

1. TECHNICAL FIELD OF THE INVENTION

Resin composition for active energy ray hardening type optical three-dimensional molding, especially optical three-dimensional molding field which should have excellent dimensional accuracy with low volume shrinkage before and after curing and excellent mechanical properties and heat resistance.

2. Technical problem to be solved by the invention

The resin viscosity should be relatively low in view of handleability, molding speed, molding precision, etc., and the volume shrinkage at the time of curing should be low in view of the dimensional accuracy of the molding, and the mechanical strength and heat resistance should be high.

3. Summary of Solution to Invention

A predetermined organic polymer solid fine particle and / or inorganic solid fine particle are mix | blended with liquid photocurable resin.

4. Important uses of the invention

Three-dimensional sculptures with high mechanical properties, low volumetric shrinkage and excellent dimensional accuracy.

Description

Optical Stereoscopic Resin Composition

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an active energy ray-curable optical solid molded resin composition, and more particularly, to an optical three-dimensional molded resin composition having excellent dimensional accuracy with low volume shrinkage before and after curing and excellent mechanical properties and heat resistance.

Japanese Unexamined Patent Publication No. 56-144478 discloses a method for supplying a three-dimensional sculpture by supplying an amount of optical energy to a photocurable resin, and a basic practical method is proposed by Japanese Patent Application Laid-Open No. 60-247515. It became.

The same or improved technology thereafter is disclosed in Japanese Patent Laid-Open No. 62-35966, Japanese Patent Laid-Open No. 1-204915, Japanese Patent Laid-Open No. 2-113925, Japanese Patent Laid-Open No. 2-145616, Japanese Patent Laid-Open No. 2-153722 3-15520, Japanese Patent Laid-Open No. 3-21432, Japanese Patent Laid-Open No. 3-41126, and the like.

A typical example of this optical stereoforming method is to selectively irradiate a computer-controlled ultraviolet laser to obtain a desired shape on the liquid surface of a liquid photocurable resin in a container, and to cure it to a predetermined thickness, and then to apply one layer onto the cured layer. It is a method of finally obtaining a three-dimensional object by repeating the lamination operation of supplying a liquid resin of the above, and irradiating and curing to obtain a continuous cured layer as described above with an ultraviolet laser.

This optical stereoscopic molding method is easily obtained in a relatively short time even if the shape of the molded product to be manufactured is quite complicated, and has attracted particular attention in recent years.

Conventionally, as a photocurable resin used for this optical stereoforming method, modified polyurethane (methane) acrylate, oligoester acrylate, urethane acrylate, epoxy acrylate, photosensitive polyimide, amino alkyd, etc. are mentioned, In recent years, Japanese Patent Application Laid-Open No. Hei 1-204915, Hei 1-213304, Hei 2-28261, Hei 2-75617, Hei 2-145616, Hei 3-104626, Various improvement techniques are disclosed in Japanese Patent Laid-Open Nos. 3-114732 and 3-114733.

In this optical solid molding method, the photocurable resin to be used has a relatively low resin viscosity from the viewpoint of handleability, molding speed, molding precision, etc., and has a low volume shrinkage at the time of curing from the viewpoint of the dimensional accuracy of the molded product. Not only that the mechanical properties of the obtained moldings are sufficiently high, but also high heat resistance has recently been required depending on the application.

However, none of the conventional liquid-state photocurable resins described above are satisfactorily satisfactory in their general properties, particularly in dimensional accuracy.

Therefore, the present inventors have continued to improve the above-described characteristics, and as a result of mixing certain organic polymer solid particles and / or inorganic solid particles with liquid photocurable resin, the mechanical stiffness is remarkably improved and the volume shrinkage rate is increased. This unexpectedly deterioration was found and the present invention was completed.

Accordingly, a first object of the present invention is to provide an optically solid molded resin composition capable of providing a three-dimensional molded article having a preferable viscosity in molding handling, having sufficiently high mechanical properties, and having a low volumetric shrinkage, and thus having excellent dimensional accuracy. To provide.

In addition, the second object of the present invention is to maintain a desired viscosity for molding handling for a long time, and has a sufficiently high mechanical properties, excellent heat resistance and low volume shrinkage rule, thereby obtaining a three-dimensional molded article excellent in dimensional accuracy It is to provide a resin composition for optical three-dimensional molding.

The above object of the present invention is achieved by each of the following inventions.

1. Resin composition for optical three-dimensional shaping | molding which mix | blended 5-70 volume% of solid fine particles processed with 95-30 volume% of liquid photocurable resin with at least 1 sort (s) or more of silane coupling agents selected from aminosilane, epoxy silane, and acrylic silane.

2. The resin composition for optical three-dimensional shaping according to the above item 1, wherein the solid fine particles are at least one inorganic solid fine particle selected from glass beads, talc fine particles and silicon oxide fine particles.

3. The resin for optical three-dimensional molding according to item 1, wherein the solid fine particles are at least one organic polymer solid fine particles selected from a crosslinked polystyrene polymer, a crosslinked polymethacrylate polymer, a polyethylene polymer, and a polypropylene polymer. Composition.

4. The resin composition for optical solid molding according to the above 2 item, wherein the solid fine particles are inorganic solid particles having an average particle diameter of 3-70 μm.

5. The resin composition for optical solid molding according to item 3, wherein the solid fine particles are organic polymer solid fine particles having an average particle diameter of 3-70 μm.

6. The inorganic solid particles are whiskeys having a diameter of 0.3-1 μm, a length of 10-70 μm, and an aspect ratio of 10-100, and the optical solids according to the above 4 item, characterized in that 5-30 vol% of the whiskeys are blended. Molding resin composition.

7. The resin composition for optical three-dimensional shaping according to the above-mentioned 6, wherein whisca is made of at least one of an aluminum borate compound, a magnesium hydroxide compound, an aluminum oxide and a silicon oxide compound.

8. The solid composition is an organic solid fine particles having an average particle diameter of 3-70 μm and inorganic solid fine particles having an average particle diameter of 3-70 μm, wherein the resin composition for optical solid molding according to item 1 above.

9. The solid fine particles are organic polymer solid particles having an average particle diameter of 3-70 μm, inorganic solid particles having an average particle diameter of 3-70 μm, and whiskey having a diameter of 0.3-1 μm, a length of 10-70 μm, and an aspect ratio of 10-100. The resin composition for optical three-dimensional molding according to claim 1, wherein 5-30 vol.% Of this whiskey is blended.

11. Liquid resin composition comprising the ethylenically unsaturated compound as the main body, the solid fine particles are treated with an acrylic silane coupling agent, the resin composition for optical three-dimensional molding according to the above item 1.

12. The optical composition according to the above item 1, wherein the liquid photocurable resin mainly consists of an epoxy unsaturated compound, and the solid fine particles are treated with an epoxysilane-based silane coupling agent.

13. The above-mentioned items 1, 3, 5, 8, 9 and 9, wherein the organic polymer solid fine particles are polyethylene solid fine particles obtained by hybridizing 1-10% by weight of an acrylic acid compound. The resin composition for optical three-dimensional molding according to any one of claims 11 and 12.

The optical three-dimensional molded resin composition of the present invention has the above-described configuration and has a preferable viscosity for molding handling, and the optical three-dimensional molded product obtained from this composition has a low volumetric shrinkage ratio, excellent dimensional accuracy, and even sufficiently high mechanical properties. It has a characteristic.

In addition, the optical molding resin composition of the present invention contains whiskers as solid fine particles, and has a desirable viscosity for molding handling, and has a low volumetric shrinkage ratio, excellent dimensional accuracy, and sufficiently high mechanical properties of the optically integrated molded product obtained from the composition. At the same time having excellent heat resistance.

In addition, when the optical molding resin composition of the present invention contains solid particulates and whiskeys together, not only can the resin composition be stably maintained for a long time, but also the optically integrated molded product obtained from these can obtain excellent dimensional accuracy. At the same time as the load, tensile strength, tensile modulus, flexural strength, flexural modulus are remarkably improved and heat resistance is improved.

The resin composition for optical solid molding used in the present invention has at least one or more solid fine particles selected from organic polymer solid fine particles and / or inorganic solid fine particles or whiskers, so that the mechanical shrinkage and heat resistance are excellent and the volume shrinkage is unexpectedly small. Thus, a three-dimensional molded article having a superior dimensional accuracy of one layer is obtained.

In addition, in combination with whiskey, the stability of the three-dimensional molding resin composition can be maintained.

This is to enable a wide range of new application development of the optical stereoscopic sculptures in the present invention.

The organic polymer solid fine particles and / or inorganic solid fine particles used in the present invention have an average particle diameter of 3-70 μm, preferably 10-60 μm, and more preferably in the range of 15-50 μm.

In this case, the particle diameters of the organic polymer solid particles and the inorganic solid particles may be the same or different, but preferably the same.

If the average particle diameter of these solid particles is less than 3 µm, the increase in resin viscosity is unnecessarily seen and cannot be blended in the desired ratio. On the other hand, if the average particle diameter is larger than 70 µm, scattering of active energy during irradiation This happens and the precision of a molded object falls.

The whisker used in the present invention has a diameter (or width) of 0.3 µm-1 µm, preferably 0.3 µm-0.7 µm, and a length of 10-70 µm, preferably 20-50 µm.

The aspect ratio is 10-100, preferably 20-70.

When the aspect ratio of whiskey used in the present invention is less than 10, the effect of the present invention when whiskey is added, that is, the effect of improving the mechanical strength and reducing the volume shrinkage, in particular, is not obtained, and the viscosity of the resin is not necessary. Not good to rise

On the other hand, if the aspect ratio of whiskey is large, the mechanical strength improvement and the volume shrinkage reduction effect are expected, but if the aspect ratio exceeds 100, the resin viscosity becomes too high or the fluid elasticity of the resin becomes high, making the molding operation difficult. At the same time, since the length of the whisker is increased and the lateral precision of the sculpture is lowered, 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 of the solid fine particles and whiskey is 14-1: 6-1, preferably 12-1: 5-1.

Outside this range, preferable results are not obtained.

In addition, the blending ratio of the organic polymer solid particles and / or organic solid particles used in the present invention to the optically solid molded resin composition is 5-70% by volume, preferably 10-55% by volume.

When the blending ratio of these organic polymer solid particles and / or inorganic solid particles is less than 5% by volume, the effect of the present invention is not sufficiently expressed. On the other hand, when the blending ratio is more than 70% by volume, the optically solid molded resin composition The viscosity becomes too high, and as a result, the decrease in the mechanical strength of the obtained molding is not observed, and there is a difficulty in molding operation, which is not recommended.

The viscosity of the optical three-dimensional molded resin composition of the present invention is preferably 5,000 cps-100,000 cps in the case of using organic polymer solid particles and / or inorganic solid particles.

In the case of using whiskers, the viscosity of the resin composition for optical stereoscopic molding of the present invention may be lower than that in the case of using the above-mentioned solid fine particles, and can be preferably used if it is 1,000 cps or more.

In the present invention, the ratio of the organic polymer solid particles and the inorganic solid particles can be arbitrarily adjusted in the range of 9: 1-1: 9 when mixing them.

Preferably 8: 2-2: 8.

The blending ratio of the liquid photocurable resin of Whisca used in the present invention is 5-30% by volume, preferably 7-20% by volume.

When the blending ratio of the whisker is less than 5% by volume, the effect of the present invention is not sufficiently exhibited. On the other hand, when the blending ratio is more than 30% by volume, the viscosity of the optical stereoscopic resin composition is too high, making it difficult to use. However, the penetration of light is impeded and there is a problem in molding operation and cannot be used.

As the organic polymer solid fine particles used in the present invention, cross-linked polystyrene-based polymers, cross-linked polymethacrylate-based polymers, polyethylene polymers, polypropylene-based polymers, and the like can be exemplified as preferable ones, and inorganic solids used in the present invention. Examples of the fine particles include glass beads, talc fine particles, silicon oxide fine particles and the like, but examples of the organic polymer solid particles and the inorganic solid fine particles are not limited thereto, and many others are used.

The whisker used in the present invention comprises at least one or more of aluminum borate compounds, sulfur hydroxide magnesium compounds, aluminum oxide, titanium oxide compounds and silicon oxide compounds, preferably aluminum borate compounds and sulfur hydroxide phases. Magnesium compounds, aluminum oxide and titanium oxide compounds.

In the present invention, it is preferable that whiskey is contained in the optically solid resin composition, in particular, a liquid photocurable resin, but may further contain the aforementioned organic polymer solid particles and inorganic solid particles.

As the organic polymer solid particles and / or inorganic solid particles or whisca used in the present invention, those treated with a silane coupling agent are preferably used, and the organic polymer solid particles and / or inorganic solid particles treated with such a silane coupling agent or When using whiskers, particularly good mechanical strength is obtained.

As the silane coupling agent used in the present invention, aminosilane, epoxy silane, acrylic silane and the like are suitably used, but the effect of the type of the silane coupling agent depends on the liquid photocurable resin used, for example, as a liquid photocurable resin. When using a vinyl type unsaturated compound, when using an epoxy type compound, it is most effective to use an epoxy silane type silane coupling agent.

Next, in the case of using polyethylene-based polymers, polypropylene-based polymers, etc. as organic polymer solid particles, at least 1-10% by weight, preferably 5-8% by weight, of acrylic acid-based compounds Employment can obtain a preferable result.

When this acrylic acid type compound is less than 1 weight%, there is little effect of the mechanical strength expressed by the process of a silane coupling agent, and even if an acrylic acid type compound exceeds 10 weight%, there is little change in effect.

The liquid photocurable resin used in the present invention may be either a polymerizable vinyl compound or an epoxy compound, and all monomers and / or oligomers of a monofunctional compound and a polyfunctional compound are used.

These monofunctional compounds and polyfunctional compounds are not specifically limited, The typical thing of liquid photocurable resin is mentioned below.

[Polymerizable Vinyl Compound]

(1) As monofunctional compound, isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, bornyl acrylate, bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydride Oxypropyl acrylate, propylene glycol acrylate, vinylpyrrolidone, acrylamide, vinyl acetate, styrene and the like.

(2) The polyfunctional compound source is trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, 1.4-butanediol diacrylate And a relate, 1.6-hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate, and diaryl phthalate.

One or more of these monofunctional and / or polyfunctional compounds may be used alone or in 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, but as the photopolymerization initiator, 2.2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, acetophenone, benzo Phenones, xanthones, fluorenones, benzaldehydes, fluorenes, anthraquinones, triphenylamines, carbazoles, 3-methylacetophenones, mihiraketones, etc. may be exemplified, but are not limited thereto. These initiators can also be used 1 type or in combination of 2 or more types.

It is also possible to use together sensitizers, such as an amine compound, as needed.

As the thermal polymerization initiator, benzoyl peroxide, t-butyl peroxy benzoate, dicumyl peroxide, diisopropyl peroxy dicarbonate, t-butyl peroxide, azobisisobutyronitrile, and the like are typical. have.

The amount of the polymerization initiator or thermal polymerization initiator used in the present invention is 0.1 to 10% by weight, respectively, based on the vinyl compound.

Epoxy Clock Compounds

Typical examples are 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.

In the case of using these epoxy sulfides, energy-activated cation initiators such as triphenylsulfonium hexafluoroantimonate are used.

The liquid photocurable resin used for this invention may mix | blend a leveling agent, surfactant, an organic polymer compound, an organic plasticizer, fillers, such as an organic bead other than the above, and inorganic fillers, such as glass beads other than the above, if needed. good.

In the liquid photocurable resin used in the present invention, organic polymer solid particles and / or inorganic solid particles or whisca may be blended in any order, and other components may be blended as necessary, and the mixing method of each component It is not specifically limited.

As the light used in the case of optically solid-forming molding the optical three-dimensional molding resin composition of the present invention, ultraviolet rays, visible rays, infrared rays, laser lights and the like are used according to the purpose.

As a typical method of the optical stereo-molding method used for the optical stereo-molded resin composition of the present invention, light is selectively irradiated to form a cured layer so as to obtain a cured layer having a desired form in this liquid composition. An uncured liquid composition is supplied to the same, and the lamination operation of forming a new cured layer and a continuous cured layer newly by irradiating with light is repeated to finally obtain the desired three-dimensional shaped object.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example

[Synthesis of urethane acrylate oligomer]

After stirring, 1023 g of an IPDI tapolymer (Sumitomo Bayer, Dismoduul 2-4372) and dibutyltin laurate 0.076 triangulated isophorone diisocyanate in a 51 3-necked flask equipped with a cooling tube and a side pipe attachment funnel. g is added and the internal temperature is 65 ° C. with an oil bath.

420.1 g of poly neopentylene adipate (made by Asahi Denka Co., Ltd., Adeka New Ace Y9-10) is put into the side pipe attachment dropping funnel which was heated at 50 degreeC previously.

Depressurize the whole system and repeat the operation of changing to normal pressure with nitrogen gas.

The polynepentylene adipate was added dropwise for 1 hour from the dropping funnel while stirring the contents while keeping the whole system at atmospheric pressure and maintaining the temperature of the flask contents in the nitrogen atmosphere at 65 ° C.

After dropping, the contents were kept at 65 ° C. for another 1 hour and the reaction was continued under stirring.

After the temperature of the flask was cooled to 50 ° C, a mixture of 0.90 g of methylhydroquinone was homogeneously dissolved in 254.5 g of 2-hydroxyethyl acrylate in a dropping funnel, and the flask content did not exceed 55 ° C. Add dropwise at and continue the reaction under stirring for 2 hours.

The urethane acrylate oligomer obtained is taken out of the flask before the contents are warmed up.

The urethane acrylate oligomer obtained here confirmed that it was a structure represented by the following general formula (I) as a result of IR and elemental analysis.

[Formula (I)]

N has an average value of 4 and R represents the following functional groups.

N has an average value of 4 and R represents the following functional groups.

Example 1

[Combination of Optical Molding Composition]

1-320 g of urethane acrylate synthesized in the synthesis example, 1080 g of polyethylene glycol 200 diacrylate (Sartoma SR 259 manufactured by Somar Co., Ltd.) and ethoxy modified trimethylol propane in a 51 three-necked flask equipped with a stirrer, a cooling tube, and a side pipe attachment funnel. 480 g of triacrylates (Sartoma SR454, manufactured by Somar Co., Ltd.) were added thereto, and the resultant was degassed under reduced pressure.

The contents were heated to 50 ° C. and stirred and mixed for about 1 hour.

Under a sunscreen environment, 120 g of 2.2-dimethoxy-2-phenylacetophenone (made by Chiba Co., Ltd., Monogae 651) is added and mixed and stirred until dissolving them.

To the obtained resin composition was added 14 g of Superdyne V201 (manufactured by Thick Murashi Co., Ltd.) as a leveling agent and 6420 g of glass beads (50 wt% in the resin composition) having an average particle diameter of 30 µm treated with an acrylic silane coupling agent, and stirred at room temperature for one day. Announced.

The viscosity of the obtained photomodified resin composition was 14,000 cps at 25 micrometers.

The Ar laser light (output 500 mW, wavelength 36.8 µm) connected was irradiated perpendicularly to the surface of the solid-form resin composition, which was combined as described above, so that a predetermined dumbbell shape and a rectangle of 4.0 mm X 10.0 mm X 130 mm were obtained. .

After wash | cleaning and removing the resin liquid adhering to the obtained hardened | cured material, it treated with the 3KW ultraviolet-ray for 10 minutes.

The obtained test piece was measured for tensile properties and warpage characteristics according to JIS standard 6911, and for thermal deformation temperature according to JIS standard K7207.

In addition, the volume shrinkage was determined by measuring the liquid resin weight ratio and the plastic resin weight ratio.

Hereinafter, the obtained result was shown to the 1st table | surface.

Comparative Example 1

1320 g of urethane acrylate synthesized in the synthesis example, 1080 g of polyethylene glycol 200 diacrylate (Somama SR259, manufactured by Somar Co., Ltd.) and ethoxy modified trimethylolpropane tree 480 g of acrylate (Somama SR454, manufactured by Somar Co., Ltd.) was added thereto, and the resultant was degassed under reduced pressure.

The contents were heated to 50 ° C. and stirred and mixed for about 1 hour.

Under the UV-protective environment, 120 g of 2,2-dimethoxy-2-phenylacetophenone (manufactured by Chiba Chemical Co., Ltd., Monocross 651) was added and mixed and stirred until complete dissolution.

The obtained optical molding resin composition was 1550 cps at 25 degreeC.

The resin composition obtained here was made into the test piece like Example 1, and the various physical properties were measured.

The results are shown in the first table.

Example 2

An optical molding resin composition was combined in the same manner as in Example 1 using glass beads treated with an aminosilane-based coupling agent instead of the glass beads used in Example 1.

The test piece was produced like Example 1, and the physical property was measured similarly.

The results are shown in the first table.

Example 3

An optical molding resin composition was combined in the same manner as in Example 1 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.

The resin viscosity was 26,000 cps at 25 ° C.

The test piece was made like Example 1, the physical property was measured similarly, and the result was shown to the 1st table | surface.

Example 4

An optical molding resin composition was combined in the same manner as in Example 1, except that an untreated glass beads having an average particle diameter of 15 µm were used instead of the glass beads used in Example 1.

The resin viscosity was 25,000 cps at 25 ° C.

The test piece was produced like Example 1, the physical property was measured similarly, and the result was shown to the 1st table | surface.

Example 5

71 g of the leveling agent used in Example 1 (manufactured by Tadamura Oil Co., Ltd.) and a glass beads having an average particle diameter of 30 µm treated with an acrylic silane coupling agent were changed to 714 g (10 wt% in the resin composition). As in Example 1 and stirred foaming at room temperature for one day.

The viscosity of the obtained optical composition resin composition was 1700 cps at 25 degreeC.

A test piece was made in the same manner as in Example 1, and the physical properties were measured in the same manner, and the results are shown in the first table.

Example 6

Instead of glass beads used in Example 1, 2826 g of crosslinked polystyrene beads (50% by volume in liquid photocurable resin composition) having an average particle diameter of 15 µm were used, and the optical molding resin was prepared in the same manner as in Example 1 except that Superdyne 201 was not added. The composition was combined.

The resin viscosity was 45,000 cps at 25 ° C.

A test piece was made in the same manner as in Example 1, and the physical properties were measured in the same manner. The results are shown in the first table.

Example 7

Except for using the crosslinked polystyrene beads having an average particle diameter of 15 µm used in Example 6, 2826 g of a crosslinked polymethacrylate-based marble having an average particle diameter of 13 µm (50 vol% in the liquid photocurable resin composition) was used as in Example 1. The resin composition for optical molding was combined.

The resin viscosity was 30,000 cps at 25 ° C.

A test piece was made in the same manner as in Example 1, the physical properties were measured in the same manner, and the results are shown in the first table.

Example 8

Resin for photoforming was carried out in the same manner as in Example 1, except that 2358 g of polyethylene beads (50% by volume in the liquid photocurable resin composition) having an average particle diameter of 30 µm was used instead of the crosslinked polystyrene beads having an average particle diameter of 15 µm used in Example 6. The composition was combined.

The resin viscosity was 25,000 cps at 25 ° C.

A test piece was made 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 below.

Example 9

An optical molding resin composition was combined in the same manner as in Example 1 except that 2358 g of polyethylene beads (50% by volume in the liquid photocurable resin composition) having an average particle diameter of 6 µm were used instead of the polyethylene beads having an average particle diameter of 30 µm. .

The resin viscosity was 60,000 cps at 25 ° C.

A test piece was made in the same manner as in Example 1, the physical properties were measured in the same manner, and the results are shown in the first table.

Example 10

Except for using polyethylene beads having an average particle diameter of 30 µm used in Example 8, 2358 g of polyethylene beads (50% by volume in the liquid photocurable resin composition) having a 6% by weight hybridized acrylic acid having an average particle diameter of 10 µm were used. The optical molding resin composition was combined as described above.

The resin viscosity was 56,000 cps at 25 ° C.

A test piece was made as in Example 1, the physical properties were measured, and the results are shown in the first table.

Example 11

2358 g of polyethylene beads 6% by weight of hybridized acrylic acid having an average particle diameter of 10 µm treated with an acrylic silane coupling agent, instead of 6% by weight of hybridized acrylic acid with polyethylene oxide having an average particle diameter of 10 µm used in Example 10 (liquid phase In the same manner as in Example 1, except that 50 vol% of the photocurable resin composition was used, a resin composition for molding was combined.

The resin viscosity was 56,000 cps at 25 ° C.

A test piece was made in the same manner as in Example 1, the physical properties were measured, and the results are shown in the first table.

Example 12

Except for using crosslinked polystyrene beads having an average particle diameter of 15 µm used in Example 6, 2826 g of crosslinked polystyrene beads having an average particle diameter of 15 µm (50 vol% in liquid photocurable resin composition) treated with an acrylic silane coupling agent were used. The optical molding resin composition was combined in the same manner as in (1).

The resin viscosity was 46,000 cps at 25 ° C.

A test piece was made in the same manner as in Example 1, the physical properties were measured, and the results are shown in the first table.

Example 13

2826 g of crosslinked polymethacrylate beads having an average particle diameter of 20 µm treated with an acrylic silane coupling agent instead of the crosslinked polymethacrylate beads having an average particle diameter of 13 µm used in Example 7 (50% by volume in the liquid photocurable resin composition) Example 1 was similarly used and the optical molding resin composition was combined except having used.

The resin viscosity was 33,000 cps at 25 ° C.

A test piece was made in the same manner as in Example 1, the physical properties thereof were measured, and the results are shown in the first table.

Comparative Example 2

In Example 8, except that the amount of polyethylene beads having an average particle diameter of 30 µm was changed to 105 g (4% by volume in the composition), the optical molding resin composition was combined in the same manner as in Example 1.

The viscosity index was 33,000 cps at 25 ° C.

A test piece was made in the same manner as in Example 1, the physical properties thereof were measured, and the results are shown in the first table.

Comparative Example 3

In Comparative Example 2, instead of polyethylene beads having an average particle diameter of 30 µm, polystyrene beads having an average particle diameter of 6 µm were used, and the optical resin composition was combined in the same manner as in Example 1 except that 7075 g (75 vol% of the composition) was used. I tried to.

However, the fluidity of this resin composition was not at all, and thus it could not be employed as the optical molding resin composition.

[Comparative Example 4]

In Comparative Example 1, 396 g of urethane acrylate synthesized in Synthesis Example, 324 g of Satoma SR259 were used as 144 g of Satoma SR454, and the resin composition was combined in the same manner as in Comparative Example 1.

57 g of Superdyne V201 was added thereto, and 5781 g (75% by volume of resin composition) of glass beads having an average particle diameter of 30 µm were used, and the optical molding resin composition was combined in the same manner as in Example 1.

The flowability of this resin composition was extremely bad, and the viscosity was 300,000 cps or more at 25 ° C.

A test piece was made in the same manner as in Example 1, the physical properties were measured, and the results are shown in the first table.

[Table 1]

As can be seen from the first table, the volume shrinkage of the molded article of the embodiment of the present invention is very small as compared with Comparative Example 1, and the volume shrinkage is greatly improved.

In addition, the tensile modulus and the flexural modulus are remarkably improved.

In addition, it is apparent that the volumetric shrinkage rate was significantly improved and the strength was remarkably improved in the polyethylene beads mixed with acrylic acid in comparison with the polyethylene beads of Example 10.

In Comparative Examples 1 to 2, the volume shrinkage was large and the dimensional accuracy was not good, and when the amount of polyethylene beads was 75% by volume in the resin composition beyond the amount used in the present invention as in Comparative Example 3, there was no fluidity of the resin mixture. It was not usable for molding.

In addition, in Comparative Example 4, it was weak in tensile strength and flexural strength and lacked practicality.

Example 14

[Combination of Optical Molding Composition]

1320 g of urethane acrylate synthesized in the synthesis example, 1080 g of polyethylene glycol 200 diacrylate (Somama SR259 manufactured by Somar Co., Ltd.) and ethoxy modified trimethylol propane tree 480 g of acrylate (Somama SR454, manufactured by Somar Co., Ltd.) was added thereto, and the resultant was degassed under reduced pressure.

The contents were heated to 50 ° C. and stirred and mixed for about 1 hour.

Under the UV-protective environment, 120 g of 2.2-dimethoxy-2-phenylacetophenonechigagai company, monocrosslinking 651) is added and mixed and stirred until complete dissolution.

Aluminum borate whisker (diameter 0.5-0.7 μm, aspect ratio 50-70) treated with 14 g of Superdyne V201 (manufactured by Tagemori Co., Ltd.) and an acrylic silane coupling agent as a leveling agent in the obtained resin composition (Alborex YS-4: 1360g (15% by volume of the resin composition) was added and the resulting foam was stirred at room temperature.

The viscosity of the obtained optical molding resin composition was 10,600 cps at 25 degreeC.

The focused Ar laser light (output 500 mW, wavelength 368 µm) was irradiated so as to obtain a predetermined dumbbell shape and a rectangle of 4.0 X 10.0 X 130 mm perpendicular to the surface of the optical molding resin composition combined as described above.

After wash | cleaning and removing the resin liquid adhering to the obtained hardened | cured material, it treated with the 3KW ultraviolet-ray for 10 minutes.

The obtained test piece was measured for tensile properties and warpage characteristics according to JIS standard 6911, and for thermal deformation temperature according to JIS standard K7207.

In addition, the volume shrinkage was calculated | required by measuring the liquid resin specific gravity and the molding resin specific gravity.

Hereinafter, the obtained result is shown to a 2nd table | surface.

Example 15

Instead of the alborex YS-4 used in Example 14, aluminum borate whisker Alborex YS-1 (manufactured by Kochi Chemical Co., Ltd.) treated with an aluminosilane-based silane coupling agent was used in the same manner as in Example 14. The resin composition was combined.

The test piece was produced like Example 14, and the physical property was measured.

The results are shown in the second table.

Example 16

An optical molding resin composition was prepared in the same manner as in Example 14 except that aluminum boric acid whisker Alvorex Y (manufactured by Kochi Chemical Co., Ltd.), which was not treated with a coupling agent, was used instead of Alborex YS-4 used in Example 14. .

A test piece was made in the same manner as in Example 14, and the physical properties thereof were measured. The results are shown in the second table.

Example 17

[Combination of Optical Molding Composition]

1320 g of urethane acrylate synthesized in the synthesis example, 1080 g of polyethylene glycol 200 diacrylate (from Satoma SR259) manufactured by Somar Co., Ltd. 480 g of a rate (Somama SR454, manufactured by Somar Co., Ltd.) were added, and the contents were stirred and mixed for about 1 hour.

Under the UV-protective environment, 120 g of 2.2-dimethoxy-2-phenylacetonephenone (available from Chiba Co., Ltd., Monocross 651) is added and mixed and stirred until complete dissolution.

14 g of superdyne V201 (manufactured by Tadamura Yushi) as a leveling agent and 5120 g of glass beads (40 vol% in the resin composition) having an average particle diameter of 30 µm determined by the obtained resin composition as a leveling agent and boric acid treated with an acrylic silane coupling agent. 1536 g (10% by volume) of aluminum whisker (diameter 0.5-0.7 탆, aspect ratio 50-70) (Alborex YS-4, manufactured by Shigoku Chemical Co., Ltd.) was added thereto, followed by foaming with stirring for one day.

The viscosity of the obtained optical molding resin composition was 40,000 cps at 25 degreeC.

One part of this optical molding resin composition was taken into a test tube and the stability of the resin was observed. As a result, it was confirmed that the stable state was maintained for about five days, and the composition was not separated.

The focused Ar laser light (output 500 mW, wavelength 368 µm) was irradiated so as to obtain a predetermined dumbbell shape and a rectangle of 4.0 X 10.0 X 130 mm perpendicular to the surface of the resin composition for optical molding combined as described above.

After wash | cleaning and removing the resin liquid adhering to the obtained hardened | cured material, it treated with the 3KW ultraviolet-ray for 10 minutes.

Tensile characteristics and warpage characteristics of the obtained test piece were measured according to JIS standard 6911.

In addition, the volume shrinkage was calculated | required by measuring the liquid resin specific gravity and the molding resin specific gravity.

Hereinafter, the obtained result is shown to a 1st table | surface.

Example 18

An optical molding resin composition was combined in the same manner as in Example 17, except that 2253 g (40% by volume) of crosslinked polystyrene beads having an average particle diameter of 15 µm and treated with an acrylic silane coupling agent were used instead of the glass beads used in Example 17.

The resin viscosity was 48,000 cps at 25 ° C.

In addition, a test piece was made in the same manner as in Example 1, and physical properties were measured.

The results are shown in the first table.

[Comparative Example 5]

An optical molding resin composition was combined in the same manner as in Example 14 except that the addition amount of aluminum borate whiscaine alborex YS-4 in Example 14 was changed to 320 g (4% by volume of the composition).

The resin viscosity was 2300 cps at 25 ° C.

A test piece was made in the same manner as in Example 14, the physical properties were measured, and the results are shown in the second table.

Comparative Example 6

In Comparative Example 5, a combination of the optical molding resin composition was attempted in the same manner as in Example 14 except that the amount of aluminum borate whiscaine alborex YS-4 added was 4150 g (35% by volume in the composition).

The viscosity index was 43000 cps at 25 ° C.

However, this resin composition was prepared in the same manner as in Example 14, but the degree of curing was not sufficient, so there was a peeling phenomenon in the intercalator and a test piece for measuring the physical properties could not be obtained.

Comparative Example 7

In Example 14, 1133 g of silicon oxide based whiskey having an aspect ratio 3 (15 vol% in the composition) was used instead of aluminum borate alpinex YS-4, and the optical resin composition was combined in the same manner as in Example 14.

The viscosity of the resin composition was 6500 cps at 25 degreeC.

A test piece was made in the same manner as in Example 14, and the physical properties thereof were measured. The results are shown in the second table.

Comparative Example 8

In the comparative example 7, the resin liquid was combined using the silicon oxide type compound of aspect ratio 150.

Using this resin solution, a test piece was made in the same manner as in Example 14, but a beard was generated on a plurality of side surfaces, and thus a preferable molded product was not obtained.

[Table 2]

As can be seen from Table 2, the tensile strength, tensile modulus, and heat resistance of the molded article of the present invention are remarkably improved, and the volume shrinkage is less than that of Comparative Example 1, and the volume shrinkage rate is improved. Can be.

When Whisca is used in combination with Examples 17 and 18, it can be seen that the volumetric shrinkage is very low, and has excellent practicality.

In Comparative Examples 1 and 5, the volume shrinkage was large, the dimensional accuracy was not good, and the other physical properties were not changed.

In Comparative Example 7, physical properties are worse than those of the present invention in those other than the present invention having an aspect ratio of 3.

Claims (12)

The resin composition for optical three-dimensional shaping | molding which mix | blended 5-70 volume% of solid fine particles processed with 95-30 volume% of liquid photocurable resin with at least 1 sort (s) or more of silane coupling agents selected from aminosilane, epoxy silane, and acrylic silane. The resin composition for optical three-dimensional shaping according to claim 1, wherein the solid fine particles are at least one inorganic solid fine particle selected from glass beads, talc fine particles, and silicon oxide fine particles. The resin composition of claim 1, wherein the solid fine particles are at least one organic polymer solid fine particle selected from a crosslinked polystyrene polymer, a crosslinked polymethacrylate polymer, a polyethylene polymer, and a polypropylene polymer. The optical solid molding resin composition according to claim 2, wherein the solid fine particles are inorganic solid particles having an average particle diameter of 3-70 µm. The resin composition for optical three-dimensional shaping according to claim 3, wherein the solid fine particles are organic polymer solid fine particles having an average particle diameter of 3-70 μm. The optical solid molding resin composition according to claim 4, wherein the inorganic solid fine particles are whiskey having a diameter of 0.3-1 μm, a length of 10-70 μm, and an aspect ratio of 10-100. The optical composition according to claim 6, wherein the whisker is at least one of an aluminum borate compound, a magnesium hydroxide compound, an aluminum oxide, and a silicon oxide compound. The resin composition for optical three-dimensional shaping according to claim 1, wherein the solid fine particles are organic solid fine particles having an average particle diameter of 3-70 μm and inorganic solid fine particles having an average particle diameter of 3-70 μm. The method according to claim 1, wherein the solid fine particles are composed of organic polymer solid particles having an average particle diameter of 3-70 μm, inorganic solid particles having an average particle diameter of 3-70 μm, and a diameter of 0.3-1 μm, a length of 10-70 μm, and an aspect ratio of 10-100. It is Whiskey, The resin composition for optical three-dimensional shaping | molding which mix | blended 5-30 volume% of this whiskey. The resin composition for optical three-dimensional shaping | molding of Claim 1 in which the liquid pore-curable resin consists mainly of an ethylenically unsaturated compound, and solid microparticles | fine-particles were processed by the acrylsilane-type silane coupling agent. The resin composition for optical three-dimensional molding according to claim 1, wherein the liquid photocurable resin mainly consists of an epoxy unsaturated compound, and the solid fine particles are treated with an epoxysilane-based silane coupling agent. The polyethylene solid fine particles according to any one of claims 1, 3, 5, 8, 10, and 11, wherein the organic polymer solid fine particles are interpolymerized with 1-10% by weight of an acrylic acid compound. Phosphorus optical three-dimensional resin composition.