Dual Cure Epoxy Inkjet Composition

Abstract

The present invention relates to an effect pigment having optically active layers consisting of a flake of a highly reflective material with directly adjacent on one side or on both sides a layer of a semiconducting material having a bandgap of 0.1 to 3.5 eV. The effect pigment may be further coated with a coating which is optically non-active in the visible wavelength region.

Claims

1. An inkjet composition comprising: i) photo polymerization reactive compound (M) containing exactly one acryloyl group, ii) photo polymerization reactive compound (N) containing at least two acryloyl groups, iii) radical photoinitiator (R), iv) epoxy compound (D) containing at least two epoxy groups, and v) epoxy curing initiator/catalyst (C), wherein (M) is different from (D) with the proviso that epoxy compound containing exactly one acryloyl group and additionally containing at least two epoxy groups is subsumed to (D), (N) is different from (D) with the proviso that epoxy compound containing at least two acryloyl groups and additionally containing at least two epoxy groups is subsumed to (D), 25-50 mol % of the contained acryloyl groups are provided by the reactive compound (N) and the molar ratio of contained acryloyl groups to contained epoxy groups of compound (D) is 0.3 to 1.5, and the inkjet composition has 1.0-4.5 mol/kg acryloyl groups.

2. The inkjet composition according to claim 1 having 1.3-4.0 mol/kg acryloyl groups.

3. The inkjet composition according to claim 1 wherein 28-45 mol % of the contained acryloyl groups are provided by the reactive compound (N).

4. The inkjet composition according to claim 1, wherein 80-100 mol % of the reactive compound (N) are species containing not more than three acryloyl groups.

5. The inkjet composition according to claim 1, wherein the molar ratio of contained acryloyl groups to contained epoxy groups of compound (D) is 0.4 to 1.3.

6. The inkjet composition according to claim 1, wherein at least 10 wt.-% of the species of (D) are di epoxides.

7. The inkjet composition according to claim 1, wherein the radical photoinitiator (R) comprises a phosphine oxide based photo initiator.

8. The inkjet composition according to claim 1, wherein the epoxy curing initiator/catalyst (C) comprises a blocked super acid.

9. The inkjet composition according to claim 1, wherein 90-100 wt. % of the contained ingredients are species of (M), (N), (R), (D) and (C).

10. The inkjet composition according to claim 1, having a viscosity of 10-40 mPa s at 45° C., where the viscosity is measured on a thermally controlled rotational rheometer in cone-plate geometry, cone diameter: 60 mm, zero-gap distance: 0.061 mm, cone angle: 0.5°, shear-rate 600s-1, at temperatures from 40 to 60° C. with a heating ramp of 2 K/min following the DIN EN ISO 3219.

11. The inkjet composition according to claim 1, wherein the epoxy curing initiator/catalyst (C) comprises an ionic polymerization initiator.

12. The inkjet composition according to claim 1, additionally containing one or more of a stabilizer, a wetting agent, a radical polymerization inhibitor, a defoamer, and a pigment.

13. A process for printing a three-dimensional object comprising the steps of: (a) jetting an inkjet composition by means of a printing machine to form a layer in a configured pattern corresponding to the shape of the object, the inkjet composition comprising: i) photo polymerization reactive compound (M) containing exactly one acryloyl group, ii) photo polymerization reactive compound (N) containing at least two acryloyl groups, iii) radical photoinitiator (R), iv) epoxy compound (D) containing at least two epoxy groups, and v) epoxy curing initiator/catalyst (C), wherein (M) is different from (D) with the proviso that epoxy compound containing exactly one acryloyl group and additionally containing at least two epoxy groups is subsumed to (D), (N) is different from (D) with the proviso that epoxy compound containing at least two acryloyl groups and additionally containing at least two epoxy groups is subsumed to (D), 25-50 mol % of the contained acryloyl groups are provided by the reactive compound (N) and the molar ratio of contained acryloyl groups to contained epoxy groups of compound (D) is 0.3 to 1.5, and the inkjet composition has 1.0-4.5 mol/kg acryloyl groups, (b) irradiating the formed layer to form a photo-cured layer, (c) sequentially repeating steps (a) and (b) to form a plurality of photo-cured layers in order to prepare a green body of the three-dimensional object, and (d) heating the green body to post cure the three-dimensional object.

14. The process according to claim 13, further comprising printing and curing a support ink to stabilize the green body, and removing the cured support ink after step c) and before the performance of step (d) by treating with an aqueous washing liquid, wherein the cured support ink is water soluble.

15. The process according to claim 13, wherein the heating step (d) is performed in such a way that temperatures between 110 and 140 are kept at least for 5 hours.

16. The process according to claim 15, where in the heating step (d) the relevant increase of the temperature is limited to 2 K/min.

17. The process according to claim 13, wherein in step (b) the irradiation is performed by means of an UV lamp and the exposure time of each ink layer is 0.1-2 s.

18. A three-dimensional object manufactured according to the process according to claim 13.

19. A three-dimensional object manufactured from an inkjet composition comprising: i) photo polymerization reactive compound (M) containing exactly one acryloyl group, ii) photo polymerization reactive compound (N) containing at least two acryloyl groups, iii) radical photoinitiator (R), iv) epoxy compound (D) containing at least two epoxy groups, and v) epoxy curing initiator/catalyst (C), wherein (M) is different from (D) with the proviso that epoxy compound containing exactly one acryloyl group and additionally containing at least two epoxy groups is subsumed to (D), (N) is different from (D) with the proviso that epoxy compound containing at least two acryloyl groups and additionally containing at least two epoxy groups is subsumed to (D), 25-50 mol % of the contained acryloyl groups are provided by the reactive compound (N) and the molar ratio of contained acryloyl groups to contained epoxy groups of compound (D) is 0.3 to 1.5, and the inkjet composition has 1.0-4.5 mol/kg acryloyl groups.

20. The inkjet composition according to claim 1, wherein 90-100 mol % of the reactive compound (N) are species containing not more than three acryloyl groups.

21. The inkjet composition according to claim 1, wherein at least 30 wt.-% of the species of (D) are di epoxides.

22. The inkjet composition according to claim 1, wherein at least 10 wt.-% of the species of (D) are 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

23. The inkjet composition according to claim 1, wherein at least 30 wt.-% of the species of (D) are 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

24. The inkjet composition according to claim 1, wherein the radical photoinitiator (R) comprises diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and/or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

25. The inkjet composition according to claim 1, wherein the epoxy curing initiator/catalyst (C) comprises one or more of trifluormethanesulfonic acid, fluorosurfuric acid, para tuoluensoflonic acid, triflurooantimonate sulfonic acid, hexafluoroantimonate, and tetrakis(pentafluorophenyl)borate.

26. The inkjet composition according to claim 1, wherein 97-100 wt. % of the contained ingredients are species of (M), (N), (R), (D) and (C).

27. The inkjet composition according to claim 11, wherein the ionic polymerization initiator functions as a latent curing agent.

Description

EXAMPLE 1

[0122] Isobornylacrylate (IBOA) (28.95wt %), acryloyl morpholine (ACMO) (15.0 wt %), trimethylpropane triacrylate (TMPTA) (15.0 wt %), Omnirad 819 (0.6 wt %), Genorad 16 (0.25 wt %), BYK 333 (0.2 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Cyclic aliphatic Epoxy) (20.0 wt %), diglycidyl ether of bisphenol A (DGEBA) (19.2 wt %) and K-PURE® CXC1612 (0.8 wt %) were mixed and filtered over 1 μm.

[0123] The ink was inkjet UV printed and post-cured as follows: 30-130° C. at 1 K/min, 130° C./10 h, 130-160° C. at 1 K/min, 160° C./10 h, 160-190° C. at 1 K/min, 190° C./4 h, 190-30° C. at −5 K/min.

[0124] The final properties of the final object were: [0125] Tensile strength: 66 MPa [0126] Elongation at break: 2.4% [0127] E-Modulus: 3300 MPa. [0128] HDT B: 121° C.

[0129] The viscosity stability of Example 1 is measured to be as following:

TABLE-US-00001 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 1 0 15 2 18 7 21 Mol of % of all % of all functionality UV-curing curing Example 1 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 28.95 1.39 35% 21% ACMO 15.0 1.06 27% 16% TMPTA 15.0 1.52 38% 23% Cyclic 20.0 1.59 24% aliphatic Epoxy DGEBA 19.2 1.13 17%

[0130] The said inkjet composition comprises: [0131] I) mol/kg acryloyl groups of (M) and (N): 3.79 [0132] II) mol % of acryloyl groups provided by reactive compound (N): 38.2 [0133] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 1.46

EXAMPLE 2

[0134] Isobornylacrylate (15.3 wt %), acryloyl morpholine (6.5 wt %), trimethylpropane triacrylate (6.8 wt %), Omnirad 819 (1.0 wt %), Genorad 16 (0.25 wt %), BYK 333 (0.2 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (55.3 wt %), polypropylene glycol diglycidyl ether 380 (14.0 wt %) and K-PURE® CXC2689 (0.7 wt %) were mixed and filtered over 1 μm.

[0135] The ink was inkjet UV printed and post-cured as follows: 30-100° C. at 1 K/min, 100° C./1 h, 100-130° C. at 1 K/min, 130° C./2 h, 130-145° C. at 1 K/min, 145° C./2 h, 145-160° C. at 1 K/min, 160° C./2 h, 160-30° C. at −5 K/min.

[0136] The final properties of the final object were: [0137] Tensile strength: 75 MPa [0138] Elongation at break: 3.5% [0139] E-Modulus: 3100 MPa. [0140] HDT B: 148° C.

[0141] The viscosity stability of the Example 2 is measured to be as following:

TABLE-US-00002 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 2 0 17 2 19 7 25 Mol of % of all % of all functionality UV-curing curing Example 2 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 15.3 0.73 39% 10% ACMO 6.5 0.46 24%  7% TMPTA 6.8 0.69 37% 10% Cyclic 55.3 4.38 63% aliphatic Epoxy PPG380DGE 14.0 0.74 11%

[0142] The said inkjet composition comprises: [0143] I) mol/kg acryloyl groups of (M) and (N): 1.88 [0144] II) mol % of acryloyl groups provided by reactive compound (N): 36.6 [0145] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 0.37

EXAMPLE 3

[0146] Isobornylacrylate (13.3 wt %), acryloyl morpholine (6.0 wt %), trimethylpropane triacrylate (6.0 wt %), CN981 (3.9 wt %), Omnirad 819 (0.6 wt %), Genorad 16 (0.25 wt %), BYK 333 (0.2 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (69.2 wt %) and K-PURE® CXC2689 (0.56 wt %) were mixed and filtered over 1 μm.

[0147] The ink was inkjet UV printed and post-cured as follows: 30-100° C. at 1 K/min, 100° C./1 h, 100-130° C. at 1 K/min, 130° C./2 h, 130-145° C. at 1 K/min, 145° C./2 h, 145-160° C. at 1 K/min, 160° C./2 h, 160-30° C. at −5 K/min.

[0148] The final properties of the final object were: [0149] Tensile strength: 86 MPa [0150] Elongation at break: 3.5% [0151] E-Modulus: 2400 MPa. [0152] HDT B: 150° C.

[0153] The viscosity stability of the Example 3 is measured to be as following:

TABLE-US-00003 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 3 0 28 2 36 7 53 Mol of % of all % of all functionality UV-curing curing Example 3 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 13.3 0.64 37% 9% ACMO 6.0 0.43 25% 6% TMPTA 6.0 0.61 35% 8% CN981 3.9 0.05  3% 1% Cyclic 69.2 5.49 76%  aliphatic Epoxy

[0154] The said inkjet composition comprises: [0155] I) mol/kg acryloyl groups of (M) and (N): 1.71 [0156] II) mol % of acryloyl groups provided by reactive compound (N): 38.1 [0157] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 0.31

EXAMPLE 4

Synthesis of Polymer-Mixture 1: Polymer 1 in 45 wt % HDDGE

[0158] The reactive solvent 1,6-Hexanediol diglycidyl ether (620.16 g; 41.4 wt %) is placed into a reaction vessel under nitrogen atmosphere and heated to 90° C. Monomers: methylmethacrylate (190.56 g; 1.90 mol; 0.35 eq.), glycidyl methacrylate (270.60 g; 1.90 mol; 0.35 eq.), isobornyl methacrylate (362.73 g; 1.63 mol; 0.30 eq.), and initiator dimethyl-2,2′-azobisisobutyra (V601, 56.36 g; 0.24 mol; 0.045 eq.) were mixed together under nitrogen atmosphere and metered in the reaction vessel over a period of 120 min. After the metering, the reaction was continued for 120 min and V601 (12.52 g; 0.054 mol; 0.01 eq.) diluted in reactive solvent 1,6-Hexanediol diglycidyl ether (53.93 g; 3.6 wt %) under nitrogen atmosphere was dropwise added in the reaction vessel over 20 min. The reaction is continued for 120 min more and the reaction temperature is then increased to 100° C. 60 min later, the reaction is stopped, and the mixture is further used without any purification for the formulation step. The molecular weight of the synthesized polymer 1 in HDDGE matrix was measured by GPC using polystyrene standard and THF as solvent. Mn: 11100 and the PDI: 1.61. The monomer rest <1% was evaluated using HPLC.

[0159] Isobornylacrylate (29.0 wt %), acryloyl morpholine (15.0 wt %), trimethylpropane triacrylate (15.0 wt %), Omnirad 819 (0.6 wt %), Genorad 16 (0.25 wt %), BYK 333 (0.2 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (23.8 wt %), polymer-mixture 1 (15.9 wt %) and K-PURE® CXC2689 (0.3 wt %) were mixed and filtered over 1 μm.

[0160] The ink was inkjet UV printed and post-cured as follows: 30-130° C. at 1 K/min, 130° C./4 h, 130-150° C. at 1 K/min, 150° C./10 h, 150-180° C. at 1 K/min, 180° C./10 h, 180-30° C. at −5 K/min.

[0161] The final properties of the final object were: [0162] Tensile strength: 82 MPa [0163] Elongation at break: 3.7% [0164] E-Modulus: 2800 MPa. [0165] HDT B: 119° C.

[0166] The viscosity stability of the Example 4 is measured to be as following:

TABLE-US-00004 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 4 0 28 7 29 Mol of % of all % of all functionality UV-curing curing Example 4 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 29.0 1.39 35% 21% ACMO 15.0 1.06 27% 16% TMPTA 15.0 1.52 38% 23% Cyclic 23.8 1.89 28% aliphatic Epoxy Polymer1 8.7 0.20  3% HDDGE 7.1 0.62  9%

[0167] The said inkjet composition comprises: [0168] I) mol/kg acryloyl groups of (M) and (N): 3.97 [0169] II) mol % of acryloyl groups provided by reactive compound (N): 38.2 [0170] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 1.47

EXAMPLE 5-10

[0171] To screen ink and material properties of potential inkjet formulations molded specimens are cured for 30 s from each side in translucent silicon molds from the bottom at a distance of 15 cm by UV-light (LED 395 nm, 16 W/cm.sup.2). Then a thermal post-curing is carried out. Testing results of this photopolymerized and oven-cured bulk specimens are then emphasizing in a good proximity the final material performance of material jetted and post-cured formulations, even though the preparation process in the first curing-step of the interpenetrating system differs.

[0172] Example 5-10 illustrate a varying formulation ratio in a way that the degree of functional acrylate groups by (N) are within the limits of claimed dual-curing inkjet inks or beyond the bounds to highlight the correlation of printing application and material characteristics.

[0173] Isobornylacrylate, acryloyl morpholine, trimethylpropane triacrylate, Omnirad 819, Genorad 16, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and K-PURE® CXC2689 were mixed in ratios as shown in Table.

[0174] The ink was molded as described above and post-cured as follows: 30-100° C. at 1 K/min, 100° C./1 h, 100-130° C. at 1 K/min, 130° C./2 h, 130-145° C. at 1 K/min, 145° C./2 h, 145-160° C. at 1 K/min, 160° C./2 h, 160-30° C. at −5 K/min.

[0175] As shown in Table the ink and material properties vary with increasing network density due to the increase of mol % by (N). Thus, the green body strength with labelling C or D is too low and the material in green state too soft, whereas a warpage of category C or D is too high and the material has too much internal tension to print and post-cure complex three dimensional objects in a sufficient dimensional accuracy with regard to the digital file. Additionally, good final mechanical properties in terms of toughness and flexibility, of preferably 60-100 MPa tensile strength and preferably 3-5% elongation at break are only achieved by balancing out the degree of functional acrylate groups by (N).

TABLE-US-00005 TABLE 1 Example Example Example Compound (in wt % in formulation) 5 6 7 IBOA 20.1 17.7 16.3 ACMO 7.2 7.2 7.2 TMPTA 2.2 4.6 6.0 Cyclic aliphatic Epoxy 69.2 69.2 69.2 Omnirad819 0.3 0.3 0.3 Genorad16 0.25 0.25 0.25 K-Pure CXC2689 0.56 0.56 0.56 I) mol/kg acryloyl groups 1.70 1.82 1.90 II) mol % of acryloyl groups by (N) 13.1 25.5 32.0 III) molar ratio 0.31 0.33 0.35 Results Viscosity at 50° C. [mPa .Math. s] 23 24 24 Viscosity at 50° C. [mPa .Math. s] after 33 34 36 7 d at 60° C. Shore-Hardness after UV-cure A7 A19 A36 Shore-Hardness after thermal-cure D85 D86 D86 Green body strength after UV-cure C A A (40 mm × 7 mm × 2 mm) Green body strength after thermal- C A A cure (40 mm × 7 mm × 2 mm) Warpage after thermal-cure A A B Tensile strength [MPa] 28 55 63 Elongation at beak [%] 0.9 2.9 3.6 E-Modulus [MPa] 3200 3100 3100 HDT B [° C.] 157 160 163 T.sub.g [° C.] 199 201 199 Network density [mol/m.sup.3] 2300 2700 2900 Example Example Example Compound (in wt % in formulation) 8 9 10 IBOA 14.8 10.1 8.3 ACMO 7.2 7.2 7.2 TMPTA 7.5 12.2 14.0 Cyclic aliphatic Epoxy 69.2 69.2 69.2 Omnirad819 0.3 0.3 0.3 Genorad16 0.25 0.25 0.25 K-Pure CXC2689 0.56 0.56 0.56 I) mol/kg acryloyl groups 1.98 2.23 2.32 II) mol % of acryloyl groups by (N) 38.4 55.3 61.0 III) molar ratio 0.36 0.41 0.42 Results Viscosity at 50° C. [mPa .Math. s] 25 28 29 Viscosity at 50° C. [mPa .Math. s] after 37 41 44 7 d at 60° C. Shore-Hardness after UV-cure A55 A83 A81 Shore-Hardness after thermal-cure D86 D84 D86 Green body strength after UV-cure A A A (40 mm × 7 mm × 2 mm) Green body strength after thermal- A A A cure (40 mm × 7 mm × 2 mm) Warpage after thermal-cure B C D Tensile strength [MPa] 66 50 46 Elongation at beak [%] 3.8 2.8 2.4 E-Modulus [MPa] 2900 2600 2600 HDT B [° C.] 157 161 162 T.sub.g [° C.] 196 197 199 Network density [mol/m.sup.3] 3300 4600 5900

EXAMPLE 11

[0176] Isobornylacrylate (26.1 wt %), acryloyl morpholine (12.3wt %), trimethylpropane triacrylate (11.3 wt %), Omnirad 819 (0.15 wt %), Genorad 16 (0.1 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (39.0 wt %), polypropylene glycol diglycidyl ether 640 (10.0 wt %) and K-PURE® CXC2689 (1.0 wt %) were mixed.

[0177] The ink was molded as described above and post-cured as follows: 30-100° C. at 1 K/min, 100° C./1 h, 100-130° C. at 1 K/min, 130° C./2 h, 130-145° C. at 1 K/min, 145° C./2 h, 145-160° C. at 1 K/min, 160° C./2 h, 160-30° C. at −5 k/min.

[0178] 10 The final properties of the final object were: [0179] Tensile strength: 62 MPa [0180] Elongation at break: 3.0% [0181] E-Modulus: 3000 MPa. [0182] HDT B: 117° C.

[0183] The viscosity stability of the Example 11 is measured to be as following:

TABLE-US-00006 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 11 0 12 7 19 Mol of % of all % of all functionality UV-curing curing Example 11 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 26.1 1.25 38% 19% ACMO 12.3 0.87 27% 13% TMPTA 11.3 1.14 35% 17% Cyclic 39.0 3.09 46% aliphatic Epoxy PPG640DGE 10.0 0.31  5%

[0184] The said inkjet composition comprises: [0185] I) mol/kg acryloyl groups of (M) and (N): 3.26 [0186] II) mol % of acryloyl groups provided by reactive compound (N): 34.9 [0187] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 0.96

EXAMPLE 12

[0188] Isobornylacrylate (26.1 wt %), acryloyl morpholine (12.3 wt %), trimethylpropane triacrylate (11.3 wt %), Omnirad 819 (0.15 wt %), Genorad 16 (0.1 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (39.0 wt %), trimethylolpropane triglycidyl ether (10.0 wt %) and K-PURE® CXC2689 (1.0 wt %) were mixed.

[0189] The ink was molded as described above and post-cured as follows: 30-100° C. at 1 K/min, 100° C./1 h, 100-130° C. at 1 K/min, 130° C./2 h, 130-145° C. at 1 K/min, 145° C./2 h, 145-160° C. at 1 K/min, 160° C./2 h, 160-30° C. at −5 k/min.

[0190] The final properties of the final object were: [0191] Tensile strength: 54 MPa [0192] Elongation at break: 2.3% [0193] E-Modulus: 3100 MPa. [0194] HDT B: 148° C.

[0195] The viscosity stability of the Example 12 is measured to be as following:

TABLE-US-00007 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 12 0 13 7 18 Mol of % of all % of all functionality UV-curing curing Example 12 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 26.1 1.25 38% 17% ACMO 12.3 0.87 27% 12% TMPTA 11.3 1.14 35% 16% Cyclic 39.0 3.09 42% aliphatic Epoxy TMPTGE 10.0 0.99 14%

[0196] The said inkjet composition comprises: [0197] I) mol/kg acryloyl groups of (M) and (N): 3.26 [0198] II) mol % of acryloyl groups provided by reactive compound (N): 34.9 [0199] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 0.80

EXAMPLE 13

[0200] Isobornylacrylate (26.1 wt %), acryloyl morpholine (12.3 wt %), trimethylpropane triacrylate (11.3 wt %), Omnirad 819 (0.15 wt %), Genorad 16 (0.1 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (39.0 wt %), epoxidized fatty acid ester based on soy bean oil (10.0 wt %) and K-PURE® CXC2689 (1.0 wt %) were mixed.

[0201] The ink was molded as described above and post-cured as follows: 30-100° C. at 1 K/min, 100° C./1 h, 100-130° C. at 1 K/min, 130° C./2 h, 130-145° C. at 1 K/min, 145° C./2 h, 145-160° C. at 1 K/min, 160° C./2 h, 160-30° C. at −5 k/min.

[0202] The final properties of the final object were: [0203] Tensile strength: 57 MPa [0204] Elongation at break: 3.2% [0205] E-Modulus: 2800 MPa. [0206] HDT B: 150° C.

[0207] The viscosity stability of the Example 13 is measured to be as following:

TABLE-US-00008 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 13 0 17 7 19 Mol of % of all % of all functionality UV-curing curing Example 13 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 26.1 1.25 38% 18% ACMO 12.3 0.87 27% 13% TMPTA 11.3 1.14 35% 17% Cyclic 39.0 3.09 46% aliphatic Epoxy Epox. Soy 10.0 0.43  6% bean oil

[0208] The said inkjet composition comprises: [0209] I) mol/kg acryloyl groups of (M) and (N): 3.26 [0210] II) mol % of acryloyl groups provided by reactive compound (N): 34.9 [0211] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 0.92

EXAMPLE 14

[0212] Isobornylacrylate (31.3 wt %), acryloyl morpholine (14.7 wt %), trimethylpropane triacrylate (13.5 wt %), Omnirad 819 (0.18 wt %), Genorad 16 (0.12 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (20.0 wt %), diglycidyl ether of bisphenol F (19.2 wt %) and K-PURE® CXC1612 (0.8 wt %) were mixed.

[0213] The ink was molded as described above and post-cured as follows: 30-130° C. at 1 K/min, 130° C./10 h, 130-160° C. at 1 K/min, 160° C./10 h, 160-190° C. at 1 K/min, 190° C./4 h, 190-30° C. at −5 k/min.

[0214] The final properties of the final object were: [0215] Tensile strength: 36 MPa [0216] Elongation at break: 1.7% [0217] E-Modulus: 2400 MPa. [0218] HDT B: 96° C.

[0219] The viscosity stability of the Example 14 is measured to be as following:

TABLE-US-00009 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 14 0 13 7 17 Mol of % of all % of all functionality UV-curing curing Example 14 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 31.3 1.50 38% 22% ACMO 14.7 1.04 27% 15% TMPTA 13.5 1.37 35% 20% Cyclic 20.0 1.59 24% aliphatic Epoxy DGEBF 19.2 1.22 18%

[0220] The said inkjet composition comprises: [0221] I) mol/kg acryloyl groups of (M) and (N): 3.91 [0222] II) mol % of acryloyl groups provided by reactive compound (N): 34.9 [0223] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 1.39

EXAMPLE 15

[0224] Isobornylacrylate (20.9 wt %), acryloyl morpholine (9.8 wt %), trimethylpropane triacrylate (9.0 wt %), bisphenol A-glycerolate diacrylate (10.0 wt %), Omnirad 819 (0.12 wt %), Genorad 16 (0.1 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (49.5 wt %) and K-PURE® CXC2689 (0.5 wt %) were mixed.

[0225] The ink was molded as described above and post-cured as follows: 30-100° C. at 1 K/min, 100° C./1 h, 100-130° C. at 1 K/min, 130° C./2 h, 130-145° C. at 1 K/min, 145° C./2 h, 145-160° C. at 1 K/min, 160° C./2 h, 160-30° C. at −5 k/min.

[0226] The final properties of the final object were: [0227] Tensile strength: 57 MPa [0228] Elongation at break: 2.0% [0229] E-Modulus: 3500 MPa. [0230] HDT B: 162° C.

[0231] The viscosity stability of the Example 15 is measured to be as following:

TABLE-US-00010 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 15 0 23 4 26 Mol of % of all % of all functionality UV-curing curing Example 15 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 20.9 1.00 33% 14% ACMO 9.8 0.69 23% 10% TMPTA 9.0 0.91 30% 13% BisGA 10.0 0.41 14%  6% Cyclic 49.5 3.92 57% aliphatic Epoxy

[0232] The said inkjet composition comprises: [0233] I) mol/kg acryloyl groups of (M) and (N): 3.02 [0234] II) mol % of acryloyl groups provided by reactive compound (N): 43.8 [0235] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 0.77

EXAMPLE 16

[0236] Isobornylacrylate (26.1 wt %), acryloyl morpholine (12.3 wt %), trimethylpropane triacrylate (11.3 wt %), Omnirad 819 (0.15 wt %), Genorad 16 (0.1 wt %), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (27.6 wt %), polyTHF250 (21.9 wt %) and K-PURE® CXC2689 (0.5 wt %) were mixed.

[0237] The ink was molded as described above and post-cured as follows: 30-100° C. at 1 K/min, 100° C./1 h, 100-130° C. at 1 K/min, 130° C./2 h, 130-145° C. at 1 K/min, 145° C./2 h, 145-160° C. at 1 K/min, 160° C./2 h, 160-30° C. at −5 k/min.

[0238] The final properties of the final object were: [0239] Tensile strength: 28 MPa [0240] Elongation at break: 14.0% [0241] E-Modulus: 1000 MPa. [0242] HDT B: 85° C.

[0243] The viscosity stability of the Example 16 is measured to be as following:

TABLE-US-00011 Viscosity at 50° C. Formulation Time [days] at 60° C. [mPa .Math. s] Example 16 0 4 7 15 Mol of % of all % of all functionality UV-curing curing Example 16 wt % in (for 1 kg final function- function- Compound formulation formulation) alities alities IBOA 26.1 1.25 38% 17% ACMO 12.3 0.86 27% 12% TMPTA 11.3 1.14 35% 16% Cyclic 27.6 2.19 30% aliphatic Epoxy polyTHF250 21.9 1.75 24%

[0244] The said inkjet composition comprises: [0245] I) mol/kg acryloyl groups of (M) and (N): 3.26 [0246] II) mol % of acryloyl groups provided by reactive compound (N): 34.9 [0247] III) molar ratio of contained acryloyl groups (M) and (N) to contained epoxy groups of compound (D): 1.49