Active energy ray-curable resin composition and ink for three-dimensional molding support materials

Abstract

An active energy ray-curable resin composition for three-dimensional molding support materials is provided and includes 0.1 to 90% by mass of a non-polymerizable compound (A) in which inorganic groups/organic groups (I/O value) equals 0.4 to 1.8, and 10 to 99.9% by mass of a polymerizable compound (B) in which inorganic groups/organic groups (I/O value) equals 0.8 to 3.0. By using the active energy ray-curable resin composition, an ink for a support material having well-balanced inorganicity and organicity is obtained, and by using the ink, the support material is easily removed from a roughly molded product without corrosion of ink tanks, ink ejection heads, and similar objects, and a large-sized and highly accurate three-dimensional molded product is obtained.

Claims

1. An active energy ray-curable resin composition for three-dimensional molding support materials, comprising 0.1 to 90% by mass of a non-polymerizable compound (A) in which inorganic groups/organic groups (I/O value) equals 0.4 to 1.8 and 10 to 99.9% by mass of a polymerizable compound (B) in which inorganic groups/organic groups (I/O value) equals 0.8 to 3.0.

2. The active energy ray-curable resin composition according to claim 1, wherein (A) is an amide compound (a1) having one or more amide groups in a molecule.

3. The active energy ray-curable resin composition according to claim 1, wherein (A) is at least one compound selected from (a1-1) N-substituted amides and N,N-disubstituted amides represented by a general formula (1), (a1-2) N-substituted lactams represented by a general formula (2), (a1-3) β-alkoxy-N-substituted propionamides and β-alkoxy-N,N-disubstituted propionamides represented by a general formula (3), and (a1-4) β-amino-N-substituted propionamides and β-amino-N,N-disubstituted propionamides represented by a general formula (4): ##STR00003## (wherein R.sub.1 to R.sub.4 each independently represent a hydrogen atom or a C.sub.1 to C.sub.18 linear, branched, or cyclic aliphatic hydrocarbon, a hydroxy group-containing aliphatic hydrocarbon, or an aromatic hydrocarbon (excluding the case where R.sub.1, R.sub.2, and R.sub.3 are simultaneously hydrogen atoms and the case where R.sub.4 is a hydrogen atom), R.sub.5 and R.sub.9 represent a hydrogen atom or a methyl group, R.sub.6 to R.sub.8, R.sub.10 to R.sub.13 each independently represent a hydrogen atom or a C.sub.1 to C.sub.18 linear, branched, or cyclic aliphatic hydrocarbon, a hydroxy group-containing aliphatic hydrocarbon, or an aromatic hydrocarbon (excluding the case where R.sub.7 and R.sub.8 are simultaneously hydrogen atoms, the case where R.sub.10 and R.sub.11 are hydrogen atoms, and the case where R.sub.12 and R.sub.13 are simultaneously hydrogen atoms, and including the case where R.sub.2 and R.sub.3, R.sub.7 and R.sub.8, R.sub.10 and R.sub.11, or R.sub.12 and R.sub.13 form a saturated 5- to 7-membered ring (including an oxygen atom-containing ring) together with a nitrogen atom carrying them), and n in the general formula (2) represents an integer of 1 to 3).

4. The active energy ray-curable resin composition according to claim 1, wherein (A) is at least one compound selected from (a1-5) β-alkoxy-N-substituted propionamides and β-alkoxy-N,N-disubstituted propionamides represented by a general formula (5): ##STR00004## (wherein R.sub.14 represents a hydrogen atom or a methyl group, R.sub.15 represents a C.sub.1 to C.sub.18 linear or branched alkyl group, R.sub.16 and R.sub.17 each independently represent a hydrogen atom or a C.sub.1 to C.sub.6 linear or branched alkyl group (excluding the case where R.sub.16 and R.sub.17 are simultaneously hydrogen atoms, and including the case where R.sub.16 and R.sub.17 form a saturated 5- to 7-membered ring (including an oxygen atom-containing ring) together with a nitrogen atom carrying them).

5. The active energy ray-curable resin composition according to claim 1, wherein (A) is a low molecular weight compound (a2) having a melting point or a softening point of 0° C. or higher and a molecular weight of less than 2,000.

6. The active energy ray-curable resin composition according to claim 1, wherein (A) is an oligomer and/or a polymer (a3) having a glass transition temperature (Tg) of 20° C. or higher and a molecular weight of 2,000 or higher.

7. The active energy ray-curable resin composition according to claim 1, wherein (A) is one or more alcohols (a4) selected from sorbitan fatty acid esters, polyalkyleneglycol fatty acid esters, glycerin fatty acid esters, sorbitan aliphatic ethers, polyalkyleneglycol aliphatic ethers, and glycerin aliphatic ethers.

8. The active energy ray-curable resin composition according to claim 1, wherein (B) is a monomer having one or more polymerizable functional groups selected from (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, allyl groups, and maleimide groups.

9. The active energy ray-curable resin composition according to claim 1, wherein (B) is one or more monomers selected from (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-methyl-N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, N,N-bishydroxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and diacetone(meth)acrylamide.

10. A photocurable ink for a support material comprising the active energy ray-curable resin composition according to claim 1 and a photopolymerization initiator (C).

11. The photocurable ink for a support material according to claim 10 having an I/O value of 0.8 to 2.0.

12. The photocurable ink for a support material according to claim 10 that is used for inkjet type three-dimensional molding, comprising 1 to 80% by mass of (A), 20 to 99% by mass of (B), and 0 to 5% by mass of (C).

13. A three-dimensional molding photocurable ink for a model material, wherein inorganic groups/organic groups (I/O value) equals 0.4 to 0.8.

14. A three-dimensional molding ink set using a photocurable ink for a model material in which inorganic groups/organic groups (I/O value) equals 0.4 to 0.8 and a photocurable ink for a support material in which inorganic groups/organic groups (I/O value) equals 0.8 to 2.0.

15. A three-dimensional molded product that is molded by using the three-dimensional molding ink set according to claim 14.

16. A photocurable ink for a support material comprising the active energy ray-curable resin composition according to claim 1 and a photopolymerization initiator (C).

17. The photocurable ink for a support material according to claim 16 having an I/O value of 0.8 to 2.0.

18. The photocurable ink for a support material according to claim 16 that is used for inkjet type three-dimensional molding, comprising 1 to 80% by mass of (A), 20 to 99% by mass of (B), and 0 to 5% by mass of (C).

Description

EXAMPLES

(1) Hereinafter, the present invention is more specifically described based on examples and comparative examples, but is not limited thereto. In the following, “parts” and “%” are all based on mass unless otherwise specified.

(2) The abbreviations and I/O values of (A), (B), (C), and other compounds used in the examples and comparative examples are as described below.

(3) (A) Non-Polymerizable Compounds

(4) (a1) Amide Compounds

(5) a1-3-1: β-dodecyloxy-N,N-dimethylpropionamide (I/O value 0.6)

(6) a1-1-1: dimethylacetamide (I/O value 1.7)

(7) a1-3-2: β-methoxy-N,N-dimethylpropionamide (I/O value 1.8)

(8) a1-1-2: 9-octadeceneamide (I/O value 0.6)

(9) a1-2-1: N-methylpyrrolidone (I/O value 1.5)

(10) a1-3-3: β-butoxy-N,N-dimethylpropionamide (I/O value 1.2)

(11) a1-1-3: N-bis(2-hydroxyethyl)dodecanamide (AMINON L-02, produced by KAO Corporation) (I/O value 1.1)

(12) a1-2-2: N-methylcaprolactam (I/O value 1.0)

(13) a1-4-1: 3-dimethylamino-N,N-diethylpropionamide (I/O value 1.6)

(14) a1-3-4: β-octadecyloxy-N,N-dimethylpropionamide (I/O value 0.5)

(15) (a2) Low Molecular Weight Compounds

(16) a2-1: 2-butyl-2-ethyl-1,3-propanediol(butylethylpropanediol, produced by KH Neochem, Co., Ltd.) (melting point 44° C., I/O value 1.1)

(17) a2-2: 1,8-octanediol (melting point 59° C., I/O value 1.3)

(18) a2-3: 1,6-hexanediol (melting point 41° C., I/O value 1.7) (a3) Oligomers, polymers

(19) a3-1: homopolymer of N,N-dimethylacrylamide, Tg 119° C., number average molecular weight 2,100 (I/O value 1.4)

(20) a3-2: homopolymer of N-vinylpyrrolidone (B-4), Tg 164° C., number average molecular weight 15,000 (I/O value 1.2)

(21) a3-3: homopolymer of N,N-dimethylacrylamide, Tg 119° C., number average molecular weight 45,000 (I/O value 1.4)

(22) a3-4: copolymer of N,N-dimethylacrylamide and hydroxyethyl methacrylate (molar ratio 4:1), Tg 101° C., number average molecular weight 5,000 (I/O value 1.4)

(23) a3-5: copolymer of N,N-dimethylacrylamide and tetrahydrofurfuryl acrylate (molar ratio 19:1), Tg 119° C., number average molecular weight 18,000 (I/O value 1.4)

(24) a3-6: homopolymer of N,N-isopropylacrylamide, Tg 134° C., number average molecular weight 12,000 (I/O value 1.8)

(25) a3-7: copolymer of hydroxyethyl methacrylate and hydroxyethyl acrylate (molar ratio 3:2), Tg 21° C., number average molecular weight 12,000 (I/O value 1.4)

(26) a3-8: homopolymer of N-acryloylmorpholine, Tg 145° C., number average molecular weight 14,000 (I/O value 1.2)

(27) a3-9: homopolymer of N,N-diethylacrylamide, Tg 81° C., number average molecular weight 8,000 (I/O value 1.0)

(28) (a4) Alcohols

(29) a4-1: polyethylene glycol oleyl ether (PEG average molecular weight 220, NONION E-205, produced by NOF Corporation) (melting point 4° C., I/O value 0.9)

(30) a4-2: polyethylene glycol stearyl ether (PEG average molecular weight 650, NONION S-215, produced by NOF Corporation) (melting point 40° C., I/O value 1.3)

(31) a4-3: diethylene glycol mono-2-ethylhexyl ether (KYOWANOL OX20, produced by KH Neochem, Co., Ltd.) (melting point −80° C., I/O value 1.0)

(32) a4-4: sorbitan monolaurate (NONION LP-20R, produced by NOF Corporation) (melting point 13° C., I/O value 1.1)

(33) a4-5: polyethylene glycol lauryl ether (PEG average molecular weight 880, NONION K-220, produced by NOF Corporation) (Melting point 40° C., I/O value 1.5)

(34) a4-6: glyceryl monolaurate ester (melting point 40° C., I/O value 0.9)

(35) a4-7: sorbitan monooleate (NONION OP-80R, produced by NOF Corporation) (melting point 5° C., I/O value 0.8)

(36) a4-8: polyethylene glycol oleyl ether (PEG average molecular weight 1,320, NONION E-230, produced by NOF Corporation) (melting point 40° C., I/O value 1.5)

(37) (B) Polymerizable Compounds

(38) B-1: N-acryloylmorpholine (registered tradename ACMO, registered tradename Kohshylmer, produced by KJ Chemicals Corporation) (I/O value 1.2)

(39) B-2: UNIOX PKA-5009 (PEG average molecular weight 550, methoxypolyethylene glycol monoallylether, produced by NOF Corporation) (I/O value 1.2)

(40) B-3: N-(2-hydroxyethyl)acrylamide (registered tradename HEAA, registered tradename Kohshylmer, produced by KJ Chemicals Corporation) (I/O value 3.0)

(41) B-4: N-vinylpyrrolidone (I/O value 1.2)

(42) B-5: N-(2-hydroxyethyl)maleimide (I/O value 2.6)

(43) B-6: methoxy polyethylene glycol monoacrylate (PEG average molecular weight 400, NK ESTER AM90G produced by Shin-Nakamura Chemical Co., Ltd.) (I/O value 1.7)

(44) B-7: N,N-dimethylacrylamide (registered tradename DMAA, registered tradename Kohshylmer, produced by KJ Chemicals Corporation) (I/O value 1.4)

(45) (C) Photopolymerization Initiators

(46) C-1: Omnirad 184 (1-hydroxy-cyclohexyl-phenyl-ketone, produced by IGM Resins B.V.)

(47) C-2: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, produced by IGM Resins B.V.)

(48) C-3: Omnirad 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, produced by IGM Resins B.V.)

(49) C-4: Omnirad 2959 (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, produced by IGM Resins B.V.)

(50) (J) Other Additives

(51) J-1: (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy) radical

(52) J-2: acryloyl aminomethyl trimethyl ammonium bis(trifluoromethanesulfonyl)imide

(53) J-3: SURFYNOL 440 (produced by Air Products Japan)

(54) J-4: BYK 307 (polyether-modified polydimethylsiloxane, produced by BYK Chemie Japan, K.K.)

(55) J-5: EMANON 1112 (polyethylene oxide laurate (12 E.O.) adduct, produced by KAO Corporation)

(56) J-6: TEGO-Rad 2100 (silicon acrylate having a polydimethyl siloxane structure, produced by Evonik Degussa)

(57) J-7: phenothiazine

(58) Others:

(59) OD: 2-ethyl-1,3-hexanediol (octanediol, produced by KH Neochem, Co., Ltd.) (melting point−40° C., I/O value 1.3) DMF: dimethylformamide (I/O value 2.2)

(60) PEG200: polyethylene glycol having a number average molecular weight of 200 (I/O value 2.7)

(61) TGM: triethylene glycol monomethyl ether (I/O value 2.3)

(62) PEG1000: polyethylene glycol having a number average molecular weight of 1,000 (I/O value 2.0)

(63) PG: 1,2-propyleneglycol (I/O value 3.3)

(64) EDG: diethylene glycol ethyl ether (I/O value 2.1)

(65) THFA: tetrahydrofurfuryl acrylate (I/O value 0.6)

(66) TBCHA: t-butylcyclohexyl acrylate (registered tradename Kohshylmer TBCHA, produced by KJ Chemicals Corporation) (I/O value 0.3)

(67) IBXA: isobornyl acrylate (I/O value 0.3)

(68) PEA: phenoxyethyl acrylate (I/O value 0.4)

(69) Ebe150: modified bisphenol A diacrylate (EBECRYL 150, produced by Daicel Allnex Ltd.) (I/O value 0.8)

(70) ADCP: tricyclodecanedimethanol diacrylate (NK ESTER A-DCP, produced by Shin-Nakamura Chemical Co., Ltd.) (I/O value 0.4)

(71) CN991: polyester urethane acrylate (produced by Arkema K.K., number average molecular weight: 3,000) (I/O value 0.9)

(72) CN996: polyetherurethane acrylate (produced by Arkema K.K., number average molecular weight: 4,500) (I/O value 0.7)

(73) A-600: polyethylene glycol diacrylate (PEG average molecular weight 400) (NK ESTER A-600, produced by Shin-Nakamura Chemical Co., Ltd.) (I/O value 1.6)

(74) With respect to the oligomers and polymers (a3), the number average molecular weight was measured by means of high-performance liquid chromatography (using LC-10A produced by Shimadzu Corporation, a column Shodex GPC KF-806L (exclusion limit molecular weight: 2×10.sup.7, separation range: 100 to 2×10.sup.7, number of theoretical plates: 10,000 plates/unit, filler material: styrene-divinyl benzene copolymer, filler particle diameter: 10 μm) using tetrahydrofuran as an eluent), and was calculated in terms of standard polystyrene molecular weight.

Example 1 Preparation of Active Energy Ray-Curable Resin Composition (D-1)

(75) (a2-1) 0.1 parts by mass, (B-1) 50.0 parts by mass, (B-2) 49.0 parts by mass and (C-1) 0.9 parts by mass were each fed into a container and stirred at a temperature of 25° C. for 1 hour to give a homogeneous and transparent active energy ray-curable resin composition (D-1).

(76) Preparation of Examples 2 to 24 as active energy ray-curable resin compositions (D-2) to (D-24) and preparation of Comparative Examples 1 to 5 as active energy ray-curable resin compositions (G-1) to (G-5)

(77) Based on the compositions summarized in Table 1, the same operation as the one described in Example 1 was performed to give active energy ray-curable resin compositions (D-2) to (D-24) as Examples 2 to 24 and active energy ray-curable resin compositions (G-1) to (G-5) as Comparative Examples 1 to 5.

(78) TABLE-US-00001 TABLE 1 Resin (A) parts (B) parts (C) parts (J) parts I/O composition by mass by mass by mass Others by mass value Example 1 D-1 a2-1 0.1 B-1 50 C-1 0.9 — — — — 1.2 B-2 49 Example 2 D-2 a2-1 69 B-1 10 C-1 1 — — — — 1.2 a3-1 20 Example 3 D-3 a1-3-1 70 B-1 20 C-1 1 — — — — 0.8 a1-1-1 9 Example 4 D-4 a1-3-2 5 B-1 94.9 C-1 0.1 — — — — 1.2 Example 5 D-5 a3-1 10 B-1 40 C-2 5 — — — — 1.2 B-2 45 Example 6 D-6 a4-1 40 B-1 59 C-2 1 — — — — 1.1 Example 7 D-7 a1-1-1 20 B-1 50 C-2 1 EDG 9 — — 1.6 a3-2 10 B-3 10 Example 8 D-8 a1-3-1 16 B-1 70 C-1 3 — — J-1 0.1 1.0 a1-1-2 9.9 a3-3 1 Example 9 D-9 a1-3-2 30 B-1 28 C-2 1 — — J-2 1 1.4 a2-2 40 Example 10 D-10 a1-2-1 10 B-1 70 C-3 0.5 — — — — 1.2 a2-1 5 a3-4 4.5 B-4 10 Example 11 D-11 a1-3-3 48.5 B-1 20 C-1 1 — — J-3 0.5 1.2 a3-1 30 Example 12 D-12 a1-3-2 18 B-1 40 C-1 2 — — — — 1.4 a1-1-2 10 a2-3 30 Example 13 D-13 a1-3-1 50 B-3 35 C-1 0.5 — — — — 1.5 a1-2-2 10 a3-5 4.5 Example 14 D-14 a1-3-1 1 B-1 30 C-1 3 — — — — 1.1 a4-1 50 a3-6 16 Example 15 D-15 a1-1-1 10 B-1 45 C-4 0.5 — — — — 1.3 a1-4-1 10 a4-2 14 a4-3 20 a3-7 0.5 Example 16 D-16 a1-3-2 20 B-3 35 C-4 1 — — — — 2.0 a4-4 24 a3-1 20 Example 17 D-17 a1-3-2 19 B-1 50 C-1 5 — — J-4 0.5 1.3 a2-1 0.5 a3-1 25 Example 18 D-18 a1-3-2 20 B-1 50 — — — — J-1 0.1 1.4 a2-1 14.9 B-5 10 a3-5 5 Example 19 D-19 a1-3-1 15 B-1 45 C-1 1 TGM 13 J-5 1 1.3 a1-3-2 15 B-6 5 a3-1 10 Example 20 D-20 a1-3-3 25 B-1 40 C-2 2 — — J-6 0.5 1.2 a4-3 15 B-7 17.5 Example 21 D-21 a1-3-3 14 B-1 40 C-2 1 OD 9.9 J-1 0.1 1.3 a4-5 35 Example 22 D-22 a1-3-1 15 B-1 50 C-1 1.5 — — — — 1.1 a1-3-2 10 C-2 1.5 a4-1 5 a4-6 10 a3-8 7 Example 23 D-23 a1-3-4 8 B-1 55 C-1 2 — — J-1 0.1 1.0 a4-7 29.9 a3-9 5 Example 24 D-24 a1-3-2 7 B-1 40 C-2 3 — — J-1 0.1 1.3 a4-8 40 a3-9 9.9 Comparative G-1 — — B-1 20 C-2 3 DMF 57 — — 2.2 Example 1 B-3 20 Comparative G-2 — — B-1 40 C-2 3 PEG200 57 — — 2.1 Example 2 Comparative G-3 — — B-3 40 C-2 3 TGM 47 — — 2.6 Example 3 PEG1000 10 Comparative G-4 — — B-1 40 C-2 3 PG 30 — — 2.1 Example 4 EDG 27 Comparative G-5 a1-3-2 7 — — C-2 3 THFA 40 J-1 0.1 1.1 Example 5 a4-8 40 a3-9 9.9

(79) The active energy ray-curable resin compositions obtained in Examples 1 to 24 and Comparative Examples 1 to 5 were used as inks for a support material to perform three-dimensional molding in Examples 25 to 48 and Comparative Examples 6 to 10. The physical properties of the inks and support materials obtained after curing were evaluated by the methods below. The results are summarized in Table 2. The evaluation methods are as described below.

(80) Viscosity Measurement

(81) With respect to the inks for a support material used in Examples and Comparative Examples, viscosity was measured with a cone plate type viscometer (name of apparatus: RE-550 viscometer, produced by Toki Sangyo Co., Ltd.) in accordance with JIS K5600-2-3 at a temperature of 25° C.

(82) Corrosiveness

(83) With a bar coater, 40 g of each of the inks for a support material of Examples and Comparative Examples was collected in a 50 mL beaker and a 10×20×2 mm aluminum substrate (A1, A5052) was immersed in each of the inks for a support material. Thereafter, the beaker was allowed to stand in a thermo-hygrostat adjusted so as to have a temperature of 60° C. and the relative humidity of 95% for 500 hours. The aluminum substrate was subsequently removed from the ink for a support material and the surface of the aluminum substrate was visually observed to evaluate corrosiveness. The results are summarized in Table 2.

(84) (++): No corrosion observed

(85) (+): Very slight corrosion observed

(86) (+−): Slight corrosion observed

(87) (−) Corrosion observed

(88) Support Properties

(89) On a horizontally laid polymethylmethacrylate plate (PMMA plate) with a thickness of 1 mm, a cylindrical spacer with a thickness of 10 mm and an internal diameter of 20 mm was placed, 0.3 g of each of the inks for a support material of Examples and Comparative Examples was filled into the inside of the spacer, and was irradiated with a UV ray (apparatus: Inverter type conveyer system ECS-4011GX produced by Eye Graphics Co., Ltd., metal halide lamp: M04-L41 produced by Eye Graphics Co., Ltd., UV illuminance: 300 mW/cm.sup.2, integrated light intensity: 1,000 mJ/cm.sup.2) to obtain a cured thin film. Onto the thin film thus obtained, 0.3 g of the ink for a support material was added and similarly cured by UV ray irradiation, and thereby thin film lamination was performed. The same work was subsequently repeated to give a support material consisting of thin films laminated up to a thickness of 10 mm. Thereafter the Shore A hardness of the support material thus obtained was measured at room temperature (25° C.) to evaluate the support properties as described below.

(90) (++): Good support properties (Shore A hardness ≥80)

(91) (+): Sufficient support properties (80> Shore A hardness 60)

(92) (+−): Support properties to some extent, but insufficient (60> Shore A hardness ≥40)

(93) (−): No support properties (40> Shore A hardness)

(94) Moisture Resistance

(95) Onto a horizontally laid glass plate, a PET release film with a heavy release property (Polyester film E7001, produced by Toyobo, Co., Ltd.) having a thickness of 75 μm was tightly adhered, a spacer having a thickness of 1 mm with an internal size of 50 mm×20 mm was placed, each of the inks for a support material of Examples and Comparative Examples was filled into the inside of the spacer, subsequently a PET release film with a light release property (polyester film E7002, produced by Toyobo, Co., Ltd.) having a thickness of 50 μm was further superimposed thereon, and the object was similarly irradiated with a UV ray to cure the ink for a support material. Thereafter, a cured product prepared by removing the PET release films on both sides was used as a test specimen and was allowed to stand in a thermo-hygrostat adjusted so as to have a temperature of 25° C. and a relative humidity of 50% for 24 hours. The test specimen surface was visually evaluated before and after still standing.

(96) (++): Cured product after still standing did not cause moisture absorption-induced deformation.

(97) (+): Cured product after still standing slightly caused moisture absorption-induced bleedout but caused nearly no deformation.

(98) (+−): Cured product after still standing caused moisture absorption-induced bleedout to some extent and slightly caused deformation.

(99) (−): Cured product after still standing was dissolved due to moisture absorption, and caused deformation.

(100) Washing Properties

(101) On a horizontally laid PMMA plate with a thickness of 1 mm, a spacer having a thickness of 1 mm with an internal size of 50 mm×40 mm was placed. Into the inside of the spacer, 1 g of “LH 100 white” produced by Mimaki Engineering, Co., Ltd., as a curable resin composition before photocuring that formed a model material and 1 g of each of the inks for a support material of Examples and Comparative Examples were filled so as to be in contact with each other, and thereafter UV ray irradiation was similarly performed to give a roughly molded product. Thereafter, the roughly molded product thus obtained and the PMMA plate were immersed together in ion exchanged water as a washing liquid at room temperature (25° C.) and after the support material was dissolved or dispersed in water and was removed from the model material and the PMMA plate, the state of the model material and the PMMA plate was observed and the washing properties were evaluated by the following methods.

(102) (++): Support material was completely removed in less than 3 hours and oily residue was observed neither in the washing liquid nor on the PMMA plate surface.

(103) (+): Support material was completely removed in 3 to less than 10 hours and oily residue was observed neither in the washing liquid nor on the PMMA plate surface.

(104) (+−): Support material was removed in 3 to less than 24 hours but oily residue was observed in the washing liquid or on the PMMA plate surface to some extent.

(105) (−): Support material was partly remained after 24 hours.

(106) TABLE-US-00002 TABLE 2 Physical properties of inks for support Physical properties of support material material after curing Inks for support Resin Viscosity Support Moisture Washing material compositions (mPa .Math. s 25° C.) Corrosiveness properties resistance properties Example 25 E-1 D-1 50 ++ + +− +− Example 26 E-2 D-2 96 ++ +− + + Example 27 E-3 D-3 15 ++ +− + + Example 28 E-4 D-4 10 ++ + + +− Example 29 E-5 D-5 76 + + +− ++ Example 30 E-6 D-6 30 ++ +− + ++ Example 31 E-7 D-7 85 + ++ +− + Example 32 E-8 D-8 46 ++ ++ ++ +− Example 33 E-9 D-9 45 ++ + + + Example 34 E-10 D-10 78 ++ + + + Example 35 E-11 D-11 932 ++ + + + Example 36 E-12 D-12 92 ++ + ++ + Example 37 E-13 D-13 20 + + + ++ Example 38 E-14 D-14 56 ++ + ++ ++ Example 39 E-15 D-15 85 ++ ++ + ++ Example 40 E-16 D-16 60 +− + ++ ++ Example 41 E-17 D-17 98 ++ ++ ++ + Example 42 E-18 D-18 48 + ++ + ++ Example 43 E-19 D-19 53 ++ ++ ++ + Example 44 E-20 D-20 45 ++ ++ ++ + Example 45 E-21 D-21 58 ++ + ++ ++ Example 46 E-22 D-22 65 ++ ++ ++ ++ Example 47 E-23 D-23 40 ++ ++ ++ ++ Example 48 E-24 D-24 70 ++ ++ ++ ++ Comparative H-1 G-1 55 − +− − + Example 6 Comparative H-2 G-2 30 − − − + Example 7 Comparative H-3 G-3 90 − +− +− +− Example 8 Comparative H-4 G-4 66 − +− − + Example 9 Comparative H-5 G-5 40 ++ ++ ++ − Example 10

(107) As can be seen from the results summarized in Table 2, the inks for a support material of Examples 25 to 48 had a viscosity of 1,000 mPa s or lower at a temperature of 25° C. and exhibited excellent ink ejection operability. Particularly the inks for a support material except for the ink of Example 35 had a viscosity of 100 mPa.Math.s or lower and exhibited good injection properties as inkjet inks. The inks of Examples did not exhibit corrosiveness, but corrosion was observed when the inks of Comparative Examples were used. With respect to the support materials after curing, those obtained in Examples had sufficient hardness and moisture resistance and exhibited good support properties and simultaneously good washing properties in water. In contrast, the support materials obtained in Comparative Examples did not completely satisfy the requirements for the physical properties of inks and for the performance after curing since the I/O values of (A) and/or (B) were not included in the ranges specified in the present invention. Corrosion was observed particularly in Comparative Examples 8 to 10 in which the I/O value of the ink for a support material exceeded 2.0, due to too high polarity of the inks.

(108) Table 3 shows compositions and I/O values of the inks for a model material of Examples 49 to 51 according to the present invention and of a comparative example.

(109) TABLE-US-00003 TABLE 3 Composition of (C) (J) Inks for model polymerizable parts by parts by I/O material compounds mass mass value Example 49 F-1 TBCHA 60 C-2 4.6 J-1 0.3 0.4 Ebe150 25 J-6 0.1 ADCP 10 Example 50 F-2 IBXA 10 C-2 4.6 J-1 0.3 0.6 PEA 50 J-6 0.1 CN991 35 Example 51 F-3 ACMO 35 C-2 4.6 J-1 0.3 0.8 PEA 30 J-6 0.1 CN996 30 Comparative I-1 ACMO 40 C-2 4.6 J-1 0.3 1.1 Example 11 PEA 30 J-6 0.1 A-600 25

(110) The three-dimensional molding ink sets according to the present invention were obtained by combining the inks for a support material (E) and the inks for a model material (F) according to the present invention. Three-dimensional molding was performed by using the ink sets of Examples 52 to 75 and Comparative Examples 12 to 19 shown in Table 4, and the moldability was evaluated. The results are summarized in the table.

(111) Moldability

(112) On a horizontally laid PMMA plate with a thickness of 1 mm, a cylindrical spacer with a thickness of 2 mm and an internal diameter of 20 mm was placed, an ink for a support material was filled into the inside of the spacer up to a height of 1 mm, and was similarly irradiated with a UV ray to give a support material as a support. Thereafter, an ink for a support material and an ink for a model material were simultaneously filled into the inside of the spacer from left and right up to a height of 2 mm on the support material, and were similarly irradiated with a UV ray to give a roughly molded product in which a hemicylindrical support material and a hemicylindrical model material were formed on the support. The spacer was thereafter removed, and the obtained roughly molded product was immersed with the PMMA plate in ion exchanged water as a washing liquid at room temperature (25° C.). After the support material was dissolved or dispersed in water and was removed from the model material and the PMMA plate, the state of the three-dimensional molded product formed from the model material was observed and the moldability was evaluated by the following standards.

(113) (++): Hemicylindrical three-dimensional molded product was obtained, the support material contact surfaces of the three-dimensional molded product were smooth, and sharp corners were formed.

(114) (+): Hemicylindrical three-dimensional molded product was obtained, the support material contact surfaces of the three-dimensional molded product were smooth, but corners were slightly rounded.

(115) (+−): Hemicylindrical three-dimensional molded product was obtained, but the support material contact surfaces of the three-dimensional molded product were slightly rounded and corners were also rounded.

(116) (−): An ink for a support material and an ink for a model material were mixed on the contact surfaces and a target hemicylindrical three-dimensional molded product was not obtained.

(117) As can be seen from the results summarized in Table 4, when the ink sets of Examples 55 to 78 were used, molded products as designed with sharp side surfaces and sharp corners were obtained, and highly accurate molding was performed. In addition, the results show that the moldability (molding accuracy) was highest when the difference in I/O values between (E) and (F) was 0.4 to 1.0, and the moldability deteriorated as the difference increased. Further, when the difference in I/O values between (E) and (F) was 1.6 or more, almost no molded product as designed was obtained as shown in Comparative Examples 13 and 14.

(118) TABLE-US-00004 TABLE 4 Inks for Inks for model Evaluation of support material material I/O value moldability I/O value I/O value difference Moldability Example 52 E-1 1.2 F-1 0.4 0.8 ++ Example 53 E-2 1.2 F-2 0.6 0.6 ++ Example 54 E-3 0.8 F-3 0.8 0.0 +− Example 55 E-4 1.2 F-3 0.8 0.4 ++ Example 56 E-5 1.2 F-2 0.6 0.6 ++ Example 57 E-6 1.1 F-2 0.6 0.5 ++ Example 58 E-7 1.6 F-1 0.4 1.2 + Example 59 E-8 1.0 F-2 0.6 0.4 ++ Example 60 E-9 1.4 F-1 0.4 1.0 ++ Example 61 E-10 1.2 F-2 0.6 0.6 ++ Example 62 E-11 1.2 F-2 0.6 0.6 ++ Example 63 E-12 1.4 F-3 0.8 0.6 ++ Example 64 E-13 1.5 F-3 0.8 0.7 ++ Example 65 E-14 1.1 F-3 0.8 0.3 + Example 66 E-15 1.3 F-2 0.6 0.7 ++ Example 67 E-16 2.0 F-1 0.4 1.6 +− Example 68 E-17 1.3 F-2 0.6 0.7 ++ Example 69 E-18 1.4 F-2 0.6 0.8 ++ Example 70 E-19 1.3 F-3 0.8 0.5 ++ Example 71 E-20 1.2 F-2 0.6 0.6 ++ Example 72 E-21 1.3 F-2 0.6 0.7 ++ Example 73 E-22 1.1 F-1 0.4 0.7 ++ Example 74 E-23 1.0 F-1 0.4 0.6 ++ Example 75 E-24 1.3 F-1 0.4 0.9 ++ Comparative H-1 2.2 F-1 0.4 1.8 − Example 12 Comparative H-2 2.1 F-1 0.4 1.7 − Example 13 Comparative H-3 2.6 F-3 0.8 1.8 − Example 14 Comparative H-4 2.1 F-1 0.4 1.7 − Example 15 Comparative H-5 1.1 I-1 1.1 0.0 +− Example 16 Comparative E-3 0.8 I-1 1.1 −0.3 − Example 17 Comparative E-8 1.0 I-1 1.1 −0.1 − Example 18 Comparative E-23 1.0 I-1 1.1 −0.1 − Example 19

INDUSTRIAL APPLICABILITY

(119) As described above, the active energy ray-curable resin composition according to the present invention has a specific I/O value and is suitably used in forming a support material for three-dimensional molding. The active energy ray-curable resin composition and ink for a support material according to the present invention have low viscosity and excellent operability, do not cause corrosion of a molding apparatus, and is usable as a photocurable ink for a support material used in three-dimensional molding with a photocurable inkjet type 3D printer. Moreover, when a roughly molded product in which a three-dimensional molded product is supported by the support material according to the present invention is immersed in a washing liquid, the support material is efficiently removed, a finishing step is unnecessary, and a highly accurate and large-sized three-dimensional molded product is obtained.

(120) In addition, a support material formed by using an ink for a support material containing the active energy ray-curable resin composition according to the present invention has good support properties and excellent washing properties, and it is also suitable for long-time molding and large-sized product molding due to its high moisture resistance. Moreover, by using an ink set obtained by combining the ink for a support material and the ink for a model material according to the present invention, three-dimensional molding with high moldability is effectuated and a highly accurate molded product with sharp side surfaces and sharp corners is obtained. The active energy ray-curable resin composition, ink for a support material, ink for a model material, and ink set according to the present invention are preferably used in large-scaled and high-speed molding with high resolution and high performance by using 3D printers having various structures, particularly a photocurable inkjet type 3D printer.