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. Reactive curable printable composition, comprising a) at least one first polymer A comprising at least one terminal group of the general formula (I)
-A.sup.1-C(═O)—CR.sup.1═CH.sub.2  (I), wherein A.sup.1 is a divalent bonding group containing at least one heteroatom; and R.sup.1 is selected from H and C.sub.1-C.sub.4 alkyl; and, optionally, at least one terminal group of the general 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 is a divalent bonding group containing at least one heteroatom; wherein the polymer backbone of the at least one polymer A is selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof; and, optionally, b) at least one second polymer B comprising at least one terminal group of the general 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 is a divalent bonding group containing at least one heteroatom; and wherein the polymer backbone of the at least one polymer B is optionally selected from the group consisting of polyoxyalkylenes, poly(meth)acrylates, polyesters, and combinations thereof; and wherein said first polymer A comprises at least one terminal group of formula (II) and/or said composition comprises a second polymer B.

2. The reactive curable printable composition of claim 1, wherein the composition is in form of a paste and has a yield stress of greater than 25, wherein the yield stress can be calculated using the formula: ${\tau }^{\frac{1}{2}}=k_{\mathrm{oc}}^{\frac{1}{2}}+k_c^{\frac{1}{2}}{\gamma }^{\frac{1}{2}},$ wherein τ is the shear stress, k.sub.oc is the Casson yield stress, k.sub.c is the Casson plastic viscosity and γ is the shear rate.

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

4. The reactive curable printable composition of claim 1, wherein the at least one polymer A and/or the at least one polymer B has a polyoxyethylene backbone, polypropylene backbone, or polyoxyethylene-polyoxypropylene backbone.

5. The reactive curable printable composition of claim 1, wherein A.sup.1 and/or A.sup.2 comprises a substituted or unsubstituted ether, amide, carbamate, urethane, urea, imino, siloxane, carboxylate, carbamoyl, amidino, carbonate, sulfonate or sulfinate group.

6. The reactive curable printable composition of claim 1, wherein in formula (I) 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, preferably a substituted or unsubstituted (cyclo)alkylene or arylene residue with 1 to 14 carbon atoms; A.sup.11 and A.sup.12 are each independently a divalent group selected from —O—C(═O)—NH—, —NH—C(═O)O—, —NH—C(═O)—NH—, —NR″—C(═O)—NH—, —NH—C(═O)—NR″—, —NH—C(═O)—, —C(═O)—NH—, —C(═O)—O—, —O—C(═O)—, —O—C(═O)—O—, —S—C(═O)—NH—, —NH—C(═O)—S—, —C(═O)—S—, —S—C(═O)—, —S—C(═O)—S—, —C(═O)—, —S—, —O—, and —NR″—, wherein R″ can be hydrogen or a hydrocarbon moiety with 1 to 12 carbon atoms, optionally substituted; and n is 0 or 1.

7. The reactive curable printable composition of claim 6, 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 —O—C(═O)—NH—, —NH—C(═O)—NH—, and —NR″—C(═O)—NH—, preferably —O—C(═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 —NH—C(═O)O—, —NH—C(═O)—NH—, and —NH—C(═O)—NR″—.

8. The reactive curable printable composition of claim 1, 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 —O—C(═O)—NH—, —NH—C(═O)O—, —NH—C(═O)—NH—, —NR″—C(═O)—NH—, —NH—C(═O)—NR″—, —NH—C(═O)—, —C(═O)—NH—, —C(═O)—O—, —O—C(═O)—, —O—C(═O)—O—, —S—C(═O)—NH—, —NH—C(═O)—S—, —C(═O)—S—, —S—C(═O)—, —S—C(═O)—S—, —C(═O)—, —S—, —O—, and —NR″—, wherein R″ can be hydrogen or a hydrocarbon moiety with 1 to 12 carbon atoms, optionally substituted; and m is 0 or 1.

9. The reactive curable printable composition of claim 8, 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; n is 0 or 1, provided that if n is 0, A.sup.21 is a divalent group selected from —O—, —O—C(═O)—NH—, —NH—C(═O)—NH—, and —NR″—C(═O)—NH—; and provided that if n is 1, A.sup.21 is a divalent group selected from —O—, —O—C(═O)—NH—, —NH—C(═O)—NH—, and —NR″—C(═O)—NH—; R.sup.22 is a divalent substituted or unsubstituted hydrocarbon residue with 1 to 20 carbon atoms, preferably a substituted or unsubstituted (cyclo)alkylene residue or arylene residue with 1 to 14 carbon atoms; and A.sup.22 is a divalent group selected from —NH—C(═O)O—, —NH—C(═O)—NH—, and —NH—C(═O)—NR″—.

10. The reactive curable printable composition of claim 1, wherein (1) in formula (II), 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; and/or (2) R.sup.11, R.sup.21 and R.sup.23 in the general formulae (III) and/or (IV) are selected from a bond, methylene, ethylene, or n-propylene group.

11. The reactive curable printable composition of claim 1, wherein the composition further comprises c) at least one photoinitiator; d) at least one filler; and/or e) at least one catalyst.

12. The reactive curable printable composition according to claim 1, wherein the composition comprises, relative to the total weight of the composition, (1) 0.01 to 90 wt.-% or 25 to 75 wt.-%, of the at least one polymer A and, optionally, the at least one polymer B; (2) 0.01 to 5 wt.-% of the at least one photoinitiator; (3) 0.01 to 60 wt.-% of the at least one filler; and/or (4) 0.01 to 5.0 wt.-% of the at least one condensation catalyst.

13. The reactive curable printable composition according to claim 1, wherein the composition further comprises at least one reactive diluent/liquid filler.

14. Method for manufacturing a three-dimensional part by extruded filament fabrication, the method comprising: (a) printing a reactive curable printable composition according to any one of the preceding claims in a layer-by-layer manner to form the three-dimensional part; (b) curing the printed layers of the reactive curable printable composition to obtain the three-dimensional part, wherein the curing step (b) optionally comprises a first curing step comprising exposure of the printed layers to radiation and a second curing step comprising exposing the printed layers to moisture.

Description

EXAMPLES

Example 1: (Meth)Acrylate-Terminated Polymers

[0194]

TABLE-US-00003 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

[0195] 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

[0196] 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.

TABLE-US-00004 TABLE 2 (all amounts in wt.-%) Formulation 1 Formulation 2 Formulation 3 Polymer 1 99 Polymer 2 99 Polymer 3 99 Omnirad TPO-L 0.9 0.9 0.9 (photoinitiator) 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

[0197]

TABLE-US-00005 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

[0198] 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 M.sub.w 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 68000 mPa.Math.s (Anton Paar, Physica MCR 301 at 23° C., Spindle PP25).