Photo-curable compositions containing high refractive index monomers for use in 3D printing applications

Patent metadata

Field	Value
Publication number	US-12492275-B2
Application number	US-202017641847-A
Country	US
Kind code	B2
Filing date	Sep 11, 2020
Priority date	Sep 12, 2019
Publication date	Dec 9, 2025
Grant date	Dec 9, 2025

Abstract

Disclosed are high refractive index monomers for ceramic/metal 3D printing applications. The compositions disclosed herein have a higher refractive index and thus better resolution and lower scattering of the light when employed in a composition to deposit ceramic or metallic particles. The disclosed compositions also include low refractive cross-linkers selected for their good thermal decomposition and reactivity to provide good cohesion during the 3D printing.

First claim

The invention claimed is:

1 . A photo-curable composition for use in a composition suitable for three-dimensional printing, the photo-curable composition comprising:
a. a monomer composition comprising at least one monomer having a refractive index of at least 1.49, wherein the at least one monomer is selected from the group consisting of
i. at least one monomer selected from the group consisting of poly(oxy-1,2-ethanediyl), alpha-(1-oxo-2-propen-1-yl)-omega-(4-(1-methyl-1-phenylethyl)phenoxy)-, N-vinyloxazole, and N-vinylcarbazole,
ii. at least one monomer of Formula I

wherein,
Z is an ethylenically unsaturated group; X is O, S, or NH; L 1 and L 2 are each independently C 1 -C 3 alkylene, —(C 1 -C 3 alkylene)-S—(C 1 -C 3 alkylene)-, or —(C 1 -C 3 alkylene)-O—(C 1 -C 3 alkylene)-; R is hydrogen or C 1 -C 6 alkyl; R 1 and R 2 are each independently aryl, aryl (C 1 -C 6 alkylene)-, heteroaryl, or heteroaryl (C 1 -C 6 alkylene)-, each of which group is substituted with 0 to 5 substituents independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, (C 1 -C 4 alkyl)S—, C 1 -C 4 haloalkyl, and C 1 -C 4 haloalkoxy; and Y 1 and Y 2 are each independently O, S, NH, or N,
iii. at least one monomer of Formula II

wherein,
A is H or CH3, and
Q is selected from the group consisting of ethylene glycol phenyl ether, poly(ethylene glycol phenyl ether acrylate), phenyl, hexylphenoxy, hexylphenoxy, 2-phenylethyl, 4-methylphenyl, 4-methylbenzyl, 2-2-methyphenylethyl, 2-3-methylphenylethyl, 2-4-methylphenylethyl, 2-(4-propylphenyl) ethyl, 2-(4-(1-methylethyl)phenyl)ethyl, 2-(4-methoxyphenyl)ethyl, 2-(4-chlorophenyl) ethyl, 2-(2-chlorophenyl)ethyl, 2-(3-chlorophenyl)ethyl, 2-(4-chlorophenyl) ethyl, 2-(4-bromophenyl)ethyl, 2-(3-phenylphenyl)ethyl, 2-(4-phenylphenyl) ethyl), and 2-(4-benzylphenyl)ethyl or Q is a moiety that includes at least one substituted or unsubstituted heteroaromatic ring,
iv. at least one monomer of formula III,

wherein
A is H or Me,
L is a bond, C 1 -C 3 alkylene or —(CR c R d —CR′ c R′ d —O) m ;
each R c , R d , R′ c and R′ d is independently H or alkyl;
m is 2 to 10; and
Q′ corresponds to one of the following formulae:

wherein the symbol ● corresponds to the point of attachment to linker L;
b. a cross-linker; and
c. a plasticizer.

2 . The photo-curable composition of claim 1 , wherein the monomer having a refractive index of at least 1.49 is at least one selected from the group consisting of poly(oxy-1,2-ethanediyl), alpha-(1-oxo-2-propen-1-yl)-omega-(4-(1-methyl-1-phenylethyl)phenoxy)-, N-vinyloxazole and N-vinylcarbazole.

3 . The photo-curable composition of claim 1 , wherein the monomer having a refractive index of at least 1.49 is the at least one acrylate monomer of Formula I wherein Z is acryloyl or methacryloyl.

4 . The photo-curable composition of claim 3 , wherein the monomer of formula I is selected from the group consisting of 1,3-bis(2-bromophenoxy)propan-2-yl acrylate, 1,3-bis(4-bromophenoxy)propan-2-yl acrylate, 1,3-bis(3-bromophenoxy)propan-2-yl acrylate, 1,3-bis(4-methylphenylthio)-2-propyl acrylate, 1,3-bis(phenoxy)propan-2-yl acrylate, 1,3-bis(2-mercaptobenzothiazoyl)-2-propyl acrylate, 1,3-bis(benzo[d]thiazol-2-ylthio)propan-2-yl acrylate, 1,3-bis(2,4,6-tribromophenoxy)-2-propyl acrylate, 1,3-bis(phenylthio)propan-2-yl acrylate, 1,3-bis(4-bromophenylthio)propan-2-yl acrylate, 1,3-bis(3-bromophenylthio)propan-2-yl acrylate, 1,3-bis(2,4,6-tribromophenylthio)propan-2-yl acrylate, 1,3-di(10H-phenothiazin-10-yl)propan-2-yl acrylate, 1,3-bis(2-(phenylthio)ethylthio)propan-2-yl acrylate, 1-phenoxy-3-(phenylthio)propan-2-yl acrylate, 1-(4-chlorophenoxy)-3-(phenylthio)propan-2-yl acrylate, 1-(4-bromophenoxy)-3-(4-bromophenylthio)propan-2-yl acrylate, 1-(2,4,6-tribromophenoxy)-3-(2,4,6-tribromophenylthio)propan-2-yl acrylate, and 1-(2,4-dibromophenoxy)-3-(2,4-dibromophenylthio)propan-2-yl acrylate, and mixtures thereof.

5 . The photo-curable composition of claim 1 , wherein the monomer having a refractive index of at least 1.49 is the at least one monomer of Formula II.

6 . The photo-curable composition of claim 5 , wherein the monomer of formula II is selected from the group consisting of poly(ethylene glycol) phenyl ether acrylate (polyEGPEA), phenyl methacrylate, hexylphenoxy methacrylate, hexylphenoxy acrylate, 2-phenylethyl methacrylate, 4-methylphenyl methacrylate, 4-methylbenzyl methacrylate, 2-(2-methylphenyl)ethyl methacrylate, 2-(3-methylphenyl)ethyl methacrylate, 2-(4-methylphenyl)ethyl methacrylate, 2-(4-propylphenyl)ethyl methacrylate, 2-(4-(1-methylethyl)phenyl)ethyl methacrylate, 2-(4-methoxyphenyl)ethyl methacrylate, 2-(4-cyclohexylphenyl)ethyl methacrylate, 2-(2-chlorophenyl)ethyl methacrylate, 2-(3-chlorophenyl)ethyl methacrylate, 2-(4-chlorophenyl)ethyl methacrylate, 2-(4-bromophenyl)ethyl methacrylate, 2-(3-phenylphenyl)ethyl methacrylate, 2-(4-phenylphenyl)ethyl methacrylate), 2-(4-benzylphenyl)ethyl methacrylate, 2-(phenylphenoxy)ethyl acrylate, 2-phenoxyethyl acrylate, 2-(phenylthio)ethyl (meth)acrylate, (2-phenoxy-2-phenyl)ethyl (meth)acrylate, (2-phenyl-2-phenylthio)ethyl (meth)acrylate, 2-, 3-, and 4-bromophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, tetrabromophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, 2-, 3-, and 4-bromobenzyl (meth)acrylate, 2,4,6-tribromobenzyl (meth)acrylate, tetrabromobenzyl (meth)acrylate, pentabromobenzyl (meth)acrylate, 3-phenyl-2-hydroxypropyl (meth)acrylate, ortho-biphenyl (meth)acrylate, 3-(2,4-dibromophenyl)-2-hydroxypropyl (meth)acrylate, (2-hydroxy-3-phenoxy)propyl (meth)acrylate, and mixtures thereof.

7 . The photo-curable composition of claim 1 , wherein the monomer having a refractive index of at least 1.49 is the at least one monomer of formula III.

8 . The photo-curable composition of claim 7 , wherein the monomer having a refractive index of at least 1.49 comprises mono(meth)acrylate of tricyclodecane methanol of formula

wherein A is H or CH 3 .

9 . The photo-curable composition of claim 1 , wherein the cross-linker has at least two ethylenically unsaturated groups.

10 . The photo-curable composition of claim 1 , wherein the cross-linker is selected from the group consisting of ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, poly(propylene glycol) di(meth)acrylate, neopentyl glycol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acr

Assignees

• Arkema France

Inventors

• Stolz Yann
• Feillee Noemi

Classifications

• B33Y70/10

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title

• C08F2/50

  with sensitising agents · CPC title

• C08F2800/20

  as weight or mass percentages · CPC title

• C09D11/101 Primary

  Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing · CPC title

• B29C64/129

  characterised by the energy source therefor, e.g. by global irradiation combined with a mask · CPC title