Radiation curable and printable composition

Abstract

The present invention relates to radiation of dual radiation/moisture curable compositions based on (meth)acrylate- and silane-terminated polymers that can be used as 3D printing materials and provide isotropic and elastomeric properties. The invention further relates to the use thereof as 3D printing materials and printing methods using said compositions.

Claims

1. A reactive curable printable composition, comprising: (i) at least one polymer A comprising at least one terminal group of formula (I):
-A.sup.1-C(O)CR.sup.1CH.sub.2(I), wherein: A.sup.1 comprises a substituted or unsubstituted amide, carbamate, urethane, urea, imino, siloxane, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group; R.sup.1 is selected from H and C.sub.1-C.sub.4 alkyl; wherein the polymer backbone of the at least one polymer A is a polyoxyalkylene; and (ii) at least one filler that is configured to modify one or more rheological properties of the composition, wherein the composition is in a form of a paste and has a yield stress of greater than 25, wherein the yield stress is calculated using the formula: ${}^{\frac{1}{2}}=k_{\mathrm{oc}}^{\frac{1}{2}}+k_c^{\frac{1}{2}}{}^{\frac{1}{2}},$ wherein (tau) is shear stress, k.sub.oc is Casson yield stress, k.sub.c is Casson plastic viscosity and (gamma) is shear rate, wherein the shear rate and the shear stress are measured using BS EN ISO 3219:1995, wherein the measuring conditions are as follows: Geometry: 25 mm plate/plate geometry, Gap: 0.25 mm, F=0N, under nitrogen, 25 C., Shear rate 0.3-40 s.sup.1, wherein Casson's model is used for extrapolation.

2. The reactive curable printable composition of claim 1, wherein A.sup.1 is a group of formula (III):
R.sup.11-A.sup.11-(R.sup.12-A.sup.12).sub.n-R.sup.13-(III) wherein: R.sup.11, R.sup.12, and R.sup.13 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms; A.sup.11 and A.sup.12 are each independently a divalent group selected from OC(O)NH, NHC(O)O, NHC(O)NH, NRC(O)NH, NHC(O)NR, NHC(O), C(O)NH, C(O)O, OC(O), OC(O)O, SC(O)NH, NHC(O)S, -A C(O)S, SC(O), SC(O)S, C(O), S, and NR, wherein R can be hydrogen or a hydrocarbon moiety with 1 to 12 carbon atoms; and n is 0 or 1.

3. The reactive curable printable composition of claim 2, wherein: R.sup.11 is a bond or a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms; A.sup.11 is a divalent group selected from OC(O)NH, NHC(O)NH, and NRC(O)NH; R.sup.13 is a bond or a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms; n is 0 or 1, provided that if n is 1, R.sup.12 is a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms; and A.sup.12 is a divalent group selected from NHC(O)O, NHC(O)NH, and NHC(O)NR.

4. The reactive curable printable composition of claim 2, wherein R.sup.11 and R.sup.13 are selected from a bond, methylene, ethylene, or n-propylene group.

5. The reactive curable printable composition of claim 1, wherein the composition further comprises: (i) at least one photoinitiator; (ii) at least one catalyst; or (iii) a combination thereof.

6. The reactive curable printable composition of claim 5, wherein the composition comprises, relative to the total weight of the composition: (i) 0.01 to 90 wt.-% of the at least one polymer A; (ii) 0.01 to 5 wt.-% of the at least one photoinitiator; (iii) 0.01 to 60 wt.-% of the at least one filler; (iv) 0.01 to 5.0 wt.-% of the at least one catalyst; or (v) a combination thereof.

7. The reactive curable printable composition of claim 1, further comprising at least one reactive diluent and/or at least one liquid filler.

8. The reactive curable printable composition of claim 1, wherein the at least one polymer A further comprises at least one terminal group of formula (II):
-A.sup.2-SiXYZ(II), wherein X, Y, Z are, independently of one another, selected from the group consisting of a hydroxyl group and C.sub.1 to C.sub.8 alkyl, C.sub.1 to C.sub.8 alkoxy, and C.sub.1 to C.sub.8 acyloxy groups, wherein X, Y, Z are substituents directly bound with the Si atom or the two of the substituents X, Y, Z form a ring together with the Si atom to which they are bound, and at least one of the substituents X, Y, Z is selected from the group consisting of a hydroxyl group, C.sub.1 to C.sub.8 alkoxy and C.sub.1 to C.sub.8 acyloxy groups, and A.sup.2 comprises a substituted or unsubstituted ether, amide, carbamate, urethane, urea, imino, siloxane, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group.

9. The reactive curable printable composition of claim 8, wherein the at least one polymer A: (i) comprises at least two terminal groups of the formula (I) or comprises at least one terminal group of the formula (I) and at least one terminal group of the formula (II); (ii) comprises 1 to 100 mol-% of terminal groups of the formula (I) and 99 to 0 mol-% of terminal groups of the formula (II); (iii) comprises: (i) two or three terminal groups of the formula (I); or (ii) one terminal group of the formula (I) and one or two terminal groups of the formula (II); or (iii) two terminal groups of the formula (I) and one terminal group of the formula (II); (iv) is a linear polymer; or (v) any combination thereof.

10. The reactive curable printable composition of claim 1, further comprising: at least one polymer B comprising at least one terminal group of formula (II):
-A.sup.2-SiXYZ(II), wherein X, Y, Z are, independently of one another, selected from the group consisting of a hydroxyl group and C.sub.1 to C.sub.8 alkyl, C.sub.1 to C.sub.8 alkoxy, and C.sub.1 to C.sub.8 acyloxy groups, wherein X, Y, Z are substituents directly bound with the Si atom or the two of the substituents X, Y, Z form a ring together with the Si atom to which they are bound, and at least one of the substituents X, Y, Z is selected from the group consisting of a hydroxyl group, C.sub.1 to C.sub.8 alkoxy and C.sub.1 to C.sub.8 acyloxy groups; A.sup.2 comprises a substituted or unsubstituted ether, amide, carbamate, urethane, urea, imino, siloxane, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group; and wherein the polymer backbone of the at least one polymer B is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof.

11. The reactive curable printable composition of claim 1, wherein the at least one polymer A further comprises at least one terminal group of formula (II), and/or said composition further comprises at least one polymer B; wherein the at least one polymer B comprises the at least one terminal group of the formula (II), wherein the least one terminal group of the formula (II) is:
-A.sup.2-SiXYZ(II), wherein X, Y, Z are, independently of one another, selected from the group consisting of a hydroxyl group and C.sub.1 to C.sub.8 alkyl, C.sub.1 to C.sub.8 alkoxy, and C.sub.1 to C.sub.8 acyloxy groups, wherein X, Y, Z are substituents directly bound with the Si atom or the two of the substituents X, Y, Z form a ring together with the Si atom to which they are bound, and at least one of the substituents X, Y, Z is selected from the group consisting of a hydroxyl group, C.sub.1 to C.sub.8 alkoxy and C.sub.1 to C.sub.8 acyloxy groups; and A.sup.2 comprises a substituted or unsubstituted ether, amide, carbamate, urethane, urea, imino, siloxane, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group; and wherein the polymer backbone of the at least one polymer B is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof.

12. The reactive curable printable composition of claim 1, wherein the at least one polymer A, the at least one polymer B, or the combination thereof, has a polyoxypropylene backbone.

13. The reactive curable printable composition of claim 11, wherein A.sup.2 is a group of formula (IV):
R.sup.21-A.sup.21-(R.sup.22-A.sup.22).sub.m-R.sup.23-(IV) wherein: R.sup.21, R.sup.22, and R.sup.23 are independently a bond or a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms; A.sup.21 and A.sup.22 are each independently a divalent group selected from OC(O)NH, NHC(O)O, NHC(O)NH, NRC(O)NH, NHC(O)NR, NHC(O), (O)NH, C(O)O, OC(O), OC(O)O, SC(O)NH, NHC(O)S, C(O)S, SC(O), SC(O)S, C(O), S, O, and NR, wherein R can be hydrogen or a hydrocarbon moiety with 1 to 12 carbon atoms; and m is 0 or 1.

14. The reactive curable printable composition of claim 13, wherein: R.sup.21 is a bond or a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms; R.sup.23 is a bond or a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms; m is 0 or 1, provided that if m is 0, A.sup.21 is a divalent group selected from O, OC(O)NH, NHC(O)NH, and NRC(O)NH; and provided that if m is 1, A.sup.21 is a divalent group selected from O, OC(O)NH, NHC(O)NH, and NRC(O)NH; R.sup.22 is a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms; and A.sup.22 is a divalent group selected from NHC(O)O, NHC(O)NH, and NHC(O)NR.

15. The reactive curable printable composition of claim 13, wherein R.sup.21 and R.sup.23 are selected from a bond, methylene, ethylene, or n-propylene group.

16. The reactive curable printable composition of claim 11, wherein X, Y, and Z are, independently of one another, selected from a hydroxyl, a methyl, an ethyl, a methoxy, or an ethoxy group, wherein at least one of the substituents is a hydroxyl group, or a methoxy or an ethoxy group.

17. The reactive curable printable composition of claim 1, wherein the at least one filler comprises fatty acid modified chalk.

Description

EXAMPLES

Example 1: (Meth)Acrylate-Terminated Polymers

(1) TABLE-US-00001 TABLE 1 (all amounts in wt.-%) Polymer 1 Polymer 2 Polymer 3 PPG 2000 73.98 PPG 8000 92.07 PPG 12000 94.47 IPDI 16.38 5.08 3.47 Hydroxy Ethyl Methacrylate 9.57 2.78 1.98 DOTL 0.07 0.07 0.08 Total 100 100 100 DOTL: Dioctyl tin dilaurate

(2) In a first step, the polyol (PPG), the isocyanate (IPDI) and the catalyst (DOTL) were mixed for 2.5 hours at 80 C. under nitrogen at 400 U/minute. The molar ratio of OH groups to NCO groups was 1:1. After the reaction, the reaction mixtures were allowed to cool to 25 C. and then the acrylate was added (in an amount that corresponds to a molar ratio of OH (polyol):NCO:OH (acrylate) of 1:1:1. Mixing was carried out for 3 hours at 25 C. The obtained Polymers 1 to 3 were clear or slightly cloudy (Polymer 2) liquids.

Example 2: Formulations

(3) The Polymers 1 to 3 of Table 1 were used in various formulations. All amounts given are in wt.-% relative to the total weight of the composition. All formulations were tack-free after curing (with UV light). The measurement of hardness was carried out using a durometer in accordance with DIN EN ISO 868:2003. Measurements of mechanical properties (tensile test) were determined in accordance with DIN 53504:2017.

(4) TABLE-US-00002 TABLE 2 (all amounts in wt.-%) Formulation 1 Formulation 2 Formulation 3 Polymer 1 99 Polymer 2 99 Polymer 3 99 Omnirad TPO-L (photoinitiator) 0.9 0.9 0.9 DOTL 0.1 0.1 0.1 Total 100 100 100 Hardness (shore A) 74 55 48 % N/mm.sup.2 N/mm.sup.2 N/mm.sup.2 10 0.95 0.21 0.13 25 1.91 0.41 0.22 50 0.64 0.33 100 1.02 0.46 200 0.81 41 2.71 121 1.18 205 0.83

Example 3: 3D Printing Formulation Based on (Meth)Acrylate-Terminated Polymer

(5) TABLE-US-00003 TABLE 3 (all amounts in wt.-%) Component/Formulation Formulation 4 Polymer 1 46.5 Voranol 2000 PPG 14.8 Omnirad TPO-L (photoinitiator) 1 Tinuvin 328 (light stabilizer) 0.5 Viscoexcel 30 SG (fatty acid 37.2 modified chalk filler) Total 100 Tensile strength 3.64 N/mm.sup.2 Shore A 62 Printability yes Yield stress 692

Example 4: Preparation of Methacrylate- and Silane-Terminated Polymer

(6) In a first step, 72.8 wt.-% of polypropylene oxide (PPG 2000), 16.2 wt.-% of isophorone diisocyanate (IPDI) and 0.07 wt.-% of dioctyl tin dilaurate (DOTL) were mixed for 0.5 hours at 80 C. under nitrogen at 400 U/minute. The molar ratio of OH groups to NCO groups was 1:2. After the reaction, the reaction mixture was allowed to cool to 25 C. and then 6.5 wt.-% of aminopropyl trimethoxysilane (AMMO) was added, and 0.5 hours later 4.5 wt.-% of hydroxy ethyl methacrylate (HEMA) was added (in an amount that corresponds to a molar ratio of OH(from polyol):NCO:NH.sub.2(from AMMO):OH(acrylate from HEMA) of 1:2:0.5:0.48. Mixing was carried out for 4.5 hours at 25 C. The mixture of methacrylate-terminated polymer, silane-terminated polymer, and methacrylate- and silane-terminated polymer was obtained. The obtained methacrylate- and silane-terminated polymer was clear liquid with a molecular weight MW of 7400 g/mol (determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the eluent according to DIN 55672-1:2007-08) and a viscosity of 68000mPa.Math.s (Anton Paar, Physica MCR 301 at 23 C., Spindle PP25).