RESIN COMPOSITION FOR THREE-DIMENSIONAL MODELING, METHOD FOR MANUFACTURING THREE-DIMENSIONAL MODELED OBJECT, AND INORGANIC FILLER PARTICLES

Abstract

Provided is a resin composition for three-dimensional modeling to which inorganic filler particles of a sufficient amount can be added, without damaging transparency. The resin composition for three-dimensional modeling includes a curable resin and inorganic filler particles, in which the inorganic filler particles are light-transmitting particles of which a difference in refractive index nd to the curable resin after curing is ±0.02 or less, and a difference in Abbe number vd to the curable resin after curing is ±10 or less.

Claims

1: A resin composition for three-dimensional modeling, comprising a curable resin and inorganic filler particles, wherein the inorganic filler particles are light-transmitting particles of which a difference in refractive index nd to the curable resin after curing is ±0.02 or less, and a difference in Abbe number vd to the curable resin after curing is ±10 or less.

2: The resin composition for three-dimensional modeling including the curable resin and the inorganic filler particles according to claim 1, wherein maximum transmittance Tmax after curing is 10% or more.

3: The resin composition for three-dimensional modeling including the curable resin and the inorganic filler particles according to claim 1, wherein a ratio Tmax/Tmin of maximum transmittance Tmax to minimum transmittance Tmin after curing is 20 or less.

4: The resin composition for three-dimensional modeling according to claim 1, wherein the curable resin is a liquid photocurable resin.

5: The resin composition for three-dimensional modeling according to claim 1, wherein the refractive index nd of the light-transmitting particles is 1.40 to 1.90, and the Abbe number vd the light-transmitting particles is 20 to 65.

6: The resin composition for three-dimensional modeling according to claim 1, wherein the light-transmitting particles are glass beads.

7: The resin composition for three-dimensional modeling according to claim 6, wherein the glass beads having a glass composition in which a total amount of Fe.sub.2O.sub.3, NiO, Cr.sub.2O.sub.3, and CuO is 1 mass % or less are used.

8: The resin composition for three-dimensional modeling according to claim 1, wherein the light-transmitting particles are glass particles containing, in terms of mass %, SiO.sub.2 of 40 to 80%, Al.sub.2O.sub.3 of 0 to 30%, B.sub.2O.sub.3 of 0 to 20%, CaO of 0 to 25%, Na.sub.2O of 0 to 30%, K.sub.2O of 0 to 30%, Li.sub.2O of 0 to 10%, TiO.sub.2 of 0 to 15%, Nb.sub.2O.sub.5 of 0 to 20%, WO.sub.3 of 0 to 20%, and F of 0 to 10%.

9: A method for manufacturing a three-dimensional modeled object comprising: selectively irradiating a liquid layer containing a resin composition with an active energy ray to form a cured layer having a pattern; and forming a new liquid layer on the cured layer and thereafter irradiating the new liquid layer with an active energy ray to form a new cured layer having a pattern continuous with the cured layer, stacking of cured layers being repeated to obtain a three-dimensional modeled object, wherein as the resin composition, a resin composition for three-dimensional modeling according to claim 1 is used.

10: Inorganic filler particles which are used by being mixed with a curable resin, comprising glass containing, in terms of mass %, SiO.sub.2 of 40 to 80%, Al.sub.2O.sub.3 of 0 to 30%, B.sub.2O.sub.3 of 0 to 20%, CaO of 0 to 25%, Na.sub.2O of 0 to 30%, K.sub.2O of 0 to 30%, Li.sub.2O of 0 to 10%, TiO.sub.2 of 0 to 15%, Nb.sub.2O.sub.5 of 0 to 20%, WO.sub.3 of 0 to 20%, and F of 0 to 10%.

Description

EXAMPLES

Example 1

[0090] Hereinafter, the resin composition for three-dimensional modeling according to the present invention will be described based on examples. Table 1 illustrates examples (samples I to III) of the present invention.

TABLE-US-00001 TABLE 1 I II III Mixing proportion (vol %) Acrylic photocurable resin 90 70 70 Glass beads A1 10 30 Glass beads A2 30 Viscosity (Pa .Math. s) 1 2.7 2.1 Tmax transmittance 65 50 82 Tmin transmittance 50 37 62 Tmax/Tmin 1.3 1.4 1.3 Knoop hardness 15 30 30

[0091] First, isophorone diisocyanate, morpholine acrylamide, and dibutyltin dilaurate were heated by an oil bath. A solution in which methylhydroquinone was uniformly mixed and dissolved was put into glycerin monomethacrylate monoacrylate, was stirred and mixed, and was reacted. A propylene oxide 4-mole adduct of pentaerythritol (4 hydroxyl groups of pentaerythritol to which 1 mole of propylene oxide was respectively added) was added thereto, and was reacted, and a reaction product including urethane acrylate oligomer and morpholine acrylamide was manufactured.

[0092] Morpholine acrylamide, and dicyclopentanyl diacrylate were added to the obtained urethane acrylate oligomer and morpholine acrylamide. Furthermore, 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) was added thereto, and a colorless and transparent acrylic photocurable resin was obtained. In the acrylic photocurable resin, the viscosity was 1 Pa.Math.s, the refractive index nd after curing was 1.5103, Abbe number vd was 51.2, and Knoop hardness was 11.

[0093] Glass beads A1 and A2 were manufactured in the following manner. After a raw material which was blended so as to be glass containing SiO.sub.2 of 50.3%, B.sub.2O.sub.3 of 7%, Al.sub.2O.sub.3 of 7.9%, K.sub.2O of 8.5%, Sb.sub.2O.sub.3 of 0.4%, TiO.sub.2 of 6.6%, Nb.sub.2O.sub.5 of 0.6%, WO.sub.3 of 1.4%, and KHF.sub.2 of 17.3%, by mass %, was melted, and the glass was pulverized to manufacture powder glass having an average particle diameter of 5 μm. The powder was exposed to a flame of an oxygen burner, and was formed into a sphere shape. Thereafter, the glass beads A1 having the average particle diameter of 5 μm was obtained by carrying out classification. In the same manner, the powder glass having the average particle diameter of 30 μm was made into beads, and the glass beads A2 having the average particle diameter of 30 μm was obtained. As a result of measuring the optical constant of the obtained glass beads A, the refractive index nd was 1.5111, and Abbe number vd was 51.

[0094] Subsequently, the glass beads A1 and A2 were added to the acrylic photocurable resin by the proportion illustrated in Table 1, and kneading was performed by three rollers, and a paste-shaped resin in which the glass beads were homogeneously dispersed was obtained. The paste-shaped resin was poured into a modeling box with a mouth of an inside size of 30 mm×30 mm, made of Teflon (registered trademark). Thereafter, the paste-shaped resin was irradiated with the light having 500 mW and a wavelength of 364 nm, and the curing was performed at 80° C.

[0095] A plate material obtained in this way had high mechanical strength, and was excellent in transparency. Therefore, if the compositions of samples I to III are used, and the three-dimensional modeled object is manufactured by the stereolithography, it is possible to obtain the modeled object with high strength and high transparency.

[0096] In the photocurable resin and the glass beads, the refractive index nd and Abbe number vd were values measured by a precise refractive index meter (KPR-2000 manufactured by Shimadzu Corporation).

[0097] The viscosity of the photocurable resin was measured by a Brookfield viscometer (DV-3).

[0098] Regarding the transmittance, in a case where mirror polishing was performed on both surfaces of the three-dimensional modeled object by a wall thickness of 1 mm, the maximum transmission wavelength was assumed to be max, and the maximum transmission wavelength was assumed to be Tmin in the transmission wavelengths of 400 nm to 800 nm.

[0099] The hardness was measured by using Knoop hardness meter under the load of 50 g.

Example 2

[0100] Table 2 illustrates an example (sample IV) of the present invention.

TABLE-US-00002 TABLE 2 IV Mixing proportion (vol %) Epoxy photocurable resin 70 Glass beads B 30 Viscosity (Pa .Math. s) 2.8 Tmax transmittance 49 Tmin transmittance 19 Tmax/Tmin 2.6 Knoop hardness 31

[0101] First, epoxycyclohexylmethyl, epoxycyclohexane carboxylate, butanediol diglycidyl ether, phenyl propane, trimethylolpropane triacrylate were prepared, and were stirred and mixed approximately for 1 hour. Thereafter, hexafluoroantimonate was added thereto, and an epoxy photocurable resin was manufactured. In the epoxy photocurable resin, the viscosity was 1 Pa.Math.s, the refractive index nd after curing was 1.5713, Abbe number vd was 35.7, and Knoop hardness was 12.

[0102] Glass beads B was manufactured in the following manner. After a raw material which was blended so as to be glass containing SiO.sub.2 of 53.6%, B.sub.2O.sub.3 of 4.3%, Al.sub.2O.sub.3 of 5.5%, MgO of 18.4%, CaO of 0.9%, Na.sub.2O of 0.5%, and SO.sub.3 of 16.8%, by mass %, was melted, and the glass was pulverized to manufacture powder glass having the average particle diameter of 5 The powder was exposed to the flame of the oxygen burner, and was formed into the sphere shape. Thereafter, the glass beads B having the average particle diameter of 5 was obtained by carrying out the classification. As a result of measuring the optical constant of the obtained glass beads B, the refractive index nd was 1.5852, and Abbe number vd was 39.

[0103] Subsequently, the glass beads B was added to the epoxy photocurable resin composition by the proportion illustrated in Table 2, and a sample was made in the same manner as Example 1, and the sample was cured. As a result, the obtained plate material had high mechanical strength, and was excellent in transparency. Therefore, if the composition of sample III is used, and the three-dimensional modeled object is manufactured by the stereolithography, it is possible to obtain the modeled object with high strength and high transparency.

Comparative Example 1

[0104] Table 3 illustrates a comparative example (sample V) of the present invention.

TABLE-US-00003 TABLE 3 V Mixing proportion (vol %) Acrylic photocurable resin 70 Glass beads B 30 Viscosity (Pa .Math. s) 2.8 Tmax transmittance 0 Tmin transmittance 0 Tmax/Tmin 0 Knoop hardness 30

[0105] The glass beads B manufactured in Example 2 was added to the acrylic photocurable resin used in Example 1 by the proportion illustrated in Table 3, and a sample was made in the same manner as Example 1, and the sample was cured. As a result, the obtained plate material was not matched in refractive index, and had an opaque appearance.

Comparative Example 2

[0106] Table 4 illustrates a comparative example (sample VI) of the present invention.

TABLE-US-00004 TABLE 4 VI Mixing proportion (vol %) Epoxy photocurable resin 70 Glass beads C 30 Viscosity (Pa .Math. s) 2.0 Tmax transmittance 70 Tmin transmittance 5 Tmax/Tmin 14 Knoop hardness 30

[0107] Glass beads C was manufactured in the following manner. After a raw material which was blended so as to be glass containing SiO.sub.2 of 52%, B.sub.2O.sub.3 of 7%, Al.sub.2O.sub.3 of 14.0%, MgO of 0.4%, CaO of 25%, SrO of 0.2%, Na.sub.2O of 0.6%, K.sub.2O of 0.1%, TiO.sub.2 of 0.3%, F.sub.2 of 0.2%, and Fe.sub.2O.sub.3 of 0.1%, by mass %, was melted, powder glass having the average particle diameter of 5 μm was manufactured. The powder was exposed to the flame of the oxygen burner, and was formed into the sphere shape. Thereafter, the glass beads C having the average particle diameter of 5 μm was obtained by carrying out the classification. As a result of measuring the optical constant of the obtained glass beads C, the refractive index nd was 1.5657, and Abbe number vd was 58.5.

[0108] The glass beads C was added to the epoxy photocurable resin used in Example 3 by the proportion illustrated in Table 4, and a sample was made in the same manner as Example 3, and the sample was cured. As a result, since Abbe number was not matched, the obtained plate material had the appearance which was colored with rainbow colors.

Example 4

[0109] Tables 5 and 6 illustrate examples (samples Nos. 1 to 26) of the inorganic filler particles of the present invention.

TABLE-US-00005 TABLE 5 1 2 3 4 5 6 7 8 SiO.sub.2 57.3 55.0 54.4 55.7 79.6 79.6 73.7 72.4 Al.sub.2O.sub.3 16.1 16.1 15.9 16.3 2.2 2.2 2.1 2.1 B.sub.2O.sub.3 17.0 17.0 16.8 17.2 3.1 MgO 0.0 0.0 0.0 1.8 CaO 1.5 1.5 1.5 1.5 SrO 1.7 1.7 1.7 1.7 BaO 0.7 0.7 0.7 0.7 ZnO 2.0 2.0 2.0 2.1 Li.sub.2O 0.0 0.0 1.1 Na.sub.2O 2.3 0.0 0.0 9.0 9.0 8.5 13.3 K.sub.2O 0.0 3.4 0.0 TiO.sub.2 3.6 3.6 3.6 3.7 5.8 5.8 5.5 Nb.sub.2O.sub.5 2.6 2.6 2.4 6.4 ZrO.sub.2 0.9 0.9 0.9 0.9 La.sub.2O.sub.3 Gd.sub.2O.sub.3 Ta.sub.2O.sub.5 WO.sub.3 6.9 Y.sub.2O.sub.3 Yb.sub.2O.sub.3 SnO.sub.2 Sb.sub.2O.sub.5 0.1 0.1 0.1 0.1 Si + Al + B 90.4 88.1 87.1 89.2 81.8 81.8 75.7 77.6 Na + K + Li 0.0 2.3 3.4 1.1 9.0 9.0 8.5 13.3 Ti + Nb + W 3.6 3.6 3.6 3.7 8.4 8.4 14.9 6.4 Nb + W 0.0 0.0 0.0 0.0 2.6 2.6 9.4 6.4 Ca + Mg + Zn + Sr 5.2 5.2 5.1 5.3 0.0 0.0 0.0 1.8 nd 1.512 1.514 1.512 1.518 1.520 1.527 1.523 1.528 vd 55.2 55.7 55.8 55.8 51.6 49.9 50.5 51.0 α30-300 32 36 36.3 37.1 42 43 48 9 10 11 12 13 14 15 SiO.sub.2 73.5 54 58.8 50.4 53 68 70 Al.sub.2O.sub.3 2.1 13.2 12.8 4.4 16.3 6.5 B.sub.2O.sub.3 1.6 4 16.5 9 11.2 MgO 2.9 8.1 0.3 CaO 8.6 12.9 4.6 3.5 0.2 SrO 12.3 3.7 BaO 8 0.6 1.4 ZnO 1.2 2 1.5 Li.sub.2O 0.2 0.2 2.9 Na.sub.2O 8.5 0.4 5.5 0.4 4.5 9.5 K.sub.2O 13.1 5 7.3 TiO.sub.2 1.9 7.4 6.8 9.9 2.6 2 0.1 Nb.sub.2O.sub.5 6.3 0.8 ZrO.sub.2 0.9 0.5 0.2 La.sub.2O.sub.3 2.4 Gd.sub.2O.sub.3 Ta.sub.2O.sub.5 WO.sub.3 3.4 Y.sub.2O.sub.3 Yb.sub.2O.sub.3 SnO.sub.2 Sb.sub.2O.sub.5 0.1 0.1 0.1 0.1 Si + Al + B 75.5 68.8 71.6 58.8 85.8 83.5 81.2 Na + K + Li 8.5 0.0 0.6 18.6 0.6 12.4 16.8 Ti + Nb + W 11.5 7.4 6.8 9.9 3.4 2.0 0.1 Nb + W 9.7 0.0 0.0 0.0 0.8 0.0 0.0 Ca + Mg + Zn + Sr 1.2 23.8 21.0 4.6 9.5 1.5 0.2 nd 1.529 1.590 1.585 1.583 1.523 1.516 1.516 vd 52.0 49.0 52.0 46.3 57.0 60.0 64.0 α30-300 32 40

TABLE-US-00006 TABLE 6 16 17 18 19 20 21 22 23 24 25 26 27 SiO.sub.2 59.9 44.4 53.2 65.5 51.0 70.0 50.9 74.5 76.0 40.0 23.0 26.8 Al.sub.2O.sub.3 3.0 3.5 0.5 7.6 0.5 7.9 B.sub.2O.sub.3 7.4 7.7 5.0 16.0 5.5 13.0 2.0 MgO CaO 4.7 0.2 4 15 14.4 SrO 2.0 BaO 23.8 13.5 4.5 1.5 10 ZnO 5.0 9.9 7.0 1 14 2 Li.sub.2O 2.2 6 4.8 Na.sub.2O 15.0 11.9 5.2 4.6 20.0 4.0 3.4 4.0 2.0 K.sub.2O 10.2 6.7 19.0 19.3 5.9 1.9 5.0 2.0 TiO.sub.2 9.6 11.5 8.1 7.8 4.9 3.0 2.7 0.4 13.0 Nb.sub.2O.sub.5 4.9 2.0 26.0 3.0 11.5 ZrO.sub.2 4 0.5 0.3 6.0 4.0 9.5 La.sub.2O.sub.3 3 1.4 0.2 14 12 Gd.sub.2O.sub.3 0.6 Ta.sub.2O.sub.5 WO.sub.3 4 Bi.sub.2O.sub.3 20.0 Yb.sub.2O.sub.3 F 5.4 1.6 3.5 0.5 Sb.sub.2O.sub.5 0.1 0.1 0.1 0.1 0.2 0.1 Si + Al + B 59.9 47.4 56.7 66.0 66.0 70.5 66.5 79.5 92.0 45.5 36.0 28.8 Na + K + Li 15.0 11.9 15.4 13.5 19.0 20.0 19.3 9.9 5.3 15.0 0.0 8.8 Ti + Nb + W 0.0 0.0 9.6 11.5 8.1 7.8 9.8 5.0 2.7 26.4 7.0 24.5 Nb + W 0.0 0.0 0.0 0.0 0.0 0.0 4.9 2.0 0.0 26.0 7.0 11.5 Ca + Mg + Zn + Sr 5.0 9.9 4.7 9.0 0.0 0.0 0.0 0.2 0.0 5.0 29.0 16.4 nd 1.557 1.589 1.586 1.576 1.529 1.530 1.548 1.528 1.496 1.679 1.721 1.795 vd 44.6 52.2 40.4 44.0 49.0 49.1 45.5 55.5 59.0 38.6 45.0 33.0 α30-300 95 98 36 92

[0110] Each of samples was manufactured in the following manner. First, after a raw material which was blended so as to have the composition of the table was melted, and the glass was pulverized to manufacture powder glass having the average particle diameter of 5 μm. The powder was exposed to the flame of the oxygen burner, and was formed into the sphere shape. Thereafter, the bead-shaped sample having the average particle diameter of 5 μm was obtained by carrying out the classification.

[0111] As a result of measuring the optical constant of the obtained samples, in samples Nos. 1 to 15, 17, and 20 to 24, the refractive indexes nd were 1.496 to 1.59, and Abbe numbers vd were 45.5 to 64.0, and the samples had the optical constant which was matched with that of the vinyl resin. In samples Nos. 5 to 12, 16 to 22, and 25 to 27, the refractive indexes nd were 1.520 to 1.795, and Abbe numbers vd were 33.0 to 52.2, and the samples had the optical constant which was matched with that of the epoxy resin. In samples Nos. 1 to 5, 7 to 9, 11, 13, 14, 17, and 23, the refractive indexes nd were 1.512 to 1.590, and Abbe numbers vd were 50.5 to 60.0, and the samples had the optical constant which was matched with that of the ABS resin.

[0112] The thermal expansion coefficient was measured by DILATO METER.

INDUSTRIAL APPLICABILITY

[0113] In the resin composition for three-dimensional modeling of the present invention, the optical constant of the glass beads is matched with that of the curable resin composition after curing, and if the three-dimensional modeled object is manufactured by using the stereolithography, the powder sintering method or the like, it is possible to obtain the modeled object with high transparency.

[0114] Since the optical constant of the inorganic filler particles of the present invention is matched with that of the curable resin, it is possible to obtain the transparent resin modeled body.