Curable composition comprising a photoinitiator

Patent metadata

Field	Value
Publication number	US-12351659-B2
Application number	US-202117908556-A
Country	US
Kind code	B2
Filing date	Mar 4, 2021
Priority date	Mar 4, 2020
Publication date	Jul 8, 2025
Grant date	Jul 8, 2025

Abstract

The present invention relates to a curable composition comprising an ethylenically unsaturated compound and a specific photoinitiator having dual initiation mechanisms. The invention also relates to a process for the preparation of a cured product, in particular a 3D-printed article, with this composition and to the use of this composition for obtaining an ink, a coating, a sealant, an adhesive, a molded article or a 3D-printed article. The invention further pertains to the use of a specific phosphine oxide photoinitiator in a 3D printing composition or 3D printing process.

First claim

The invention claimed is:

1. A curable composition comprising:
a) an ethylenically unsaturated compound consisting essentially of one or more (meth)acrylate-functionalized monomers and optionally one or more (meth)acrylate-functionalized oligomers; and
b) a phosphine oxide photoinitiator having both Norrish Type I and Norrish type II activity.

2. The curable composition of claim 1 , wherein the ethylenically unsaturated compound a) is selected from one or more (meth)acrylate-functionalized monomers, one or more (meth)acrylate-functionalized oligomers and mixtures thereof.

3. The curable composition of claim 2 , wherein the one or more (meth)acrylate-functionalized monomers and/or the one or more (meth)acrylate-functionalized oligomers do not comprise any amino group.

4. The curable composition of claim 2 , wherein the one or more (meth)acrylate functionalized monomers have 1 to 6 (meth)acrylate groups and a molecular weight of less than 600 g/mol.

5. The curable composition of claim 2 , wherein the one or more (meth)acrylate functionalized monomers comprise a mono (meth)acrylate-functionalized monomer selected from the group consisting of methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2- and 3-hydroxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2- and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy) ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate: 2-phenoxyethyl (meth)acrylate; lauryl (meth)acrylate; alkoxylated phenol (meth)acrylates; alkoxylated nonylphenol (meth)acrylates; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; methoxy polyethylene glycol (meth)acrylates; hydroxyl ethyl-butyl urethane (meth)acrylates; 3-(2-hydroxyalkyl) oxazolidinone (meth)acrylates; glycerol carbonate (meth)acrylate; and combinations thereof.

6. The curable composition of claim 2 , wherein the composition comprises 10 to 80% by weight of the one or more (meth)acrylate-functionalized monomers based on the total weight of the curable composition.

7. The curable composition of claim 2 , wherein the ethylenically unsaturated compound a) comprises the one or more (meth)acrylate-functionalized oligomers and the one or more (meth)acrylate functionalized oligomers have 1 to 18 (meth)acrylate groups and a number average molecular weight equal or more than 600 g/mol.

8. The curable composition of claim 2 , wherein the ethylenically unsaturated compound a) comprises the one or more (meth)acrylate-functionalized oligomers and the one or more (meth)acrylate-functionalized oligomers are selected from the group consisting of (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polydiene oligomers, (meth)acrylate-functionalized polycarbonate oligomers, (meth)acrylate-functionalized polyester oligomers and mixtures thereof.

9. The curable composition of claim 2 , wherein the ethylenically unsaturated compound a) comprises the one or more (meth)acrylate-functionalized oligomers and the (meth)acrylate-functionalized oligomer comprises a (meth)acrylate-functionalized urethane oligomer having two (meth)acrylate groups.

10. The curable composition of claim 2 , wherein the composition comprises 10 to 80% by weight of the one or more (meth)acrylate-functionalized oligomers based on the total weight of the curable composition.

11. The curable composition of claim 1 , wherein the ethylenically unsaturated compound a) consists essentially of a mixture of one or more (meth)acrylate-functionalized monomers and one or more (meth)acrylate-functionalized oligomers.

12. The curable composition of claim 1 , wherein the phosphine oxide photoinitiator b) has the following formula (I):

wherein
R 1 is C 1-20 alkyl, C 7 -C 20 alkylaryl or an optionally substituted phenyl or polyphenyl;
R 2 , R 3 , R 4 and R 5 are independently hydrogen, halogen, C 1-20 alkyl, —OR 6 or CF 3 and two of radicals R 2 , R 3 , R 4 and R 5 may together form C 1-20 alkylene which can be interrupted by O, S or NR 7 ;
R 6 is hydrogen, C 1-20 alkyl, C 2-20 alkenyl, C 3 -C 8 cycloalkyl, phenyl, benzyl or C 2-20 alkyl which is interrupted once or more than once by O or S and which is unsubstituted or is substituted by OH and/or SH;
R 7 is hydrogen, phenyl, C 1-12 alkyl or C 2-12 alkyl which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH and/or SH;
R 8 and R 9 are independently an optionally substituted group selected from C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 2-20 alkenyl, C 3 -C 8 cycloalkyl, C 6 -C 12 aryl, C 7 -C 20 alkylaryl and C 5 -C 9 heteroaryl;
A and B are independently a bond, —(CH 2 ) n — or —C(═O)—;
n is 1 to 10.

13. The curable composition of claim 12 , wherein
R 1 is phenyl;
R 2 , R 3 and R 4 are independently hydrogen, Cl, methyl or methoxy;
R 5 is hydrogen;
-A-R 8 and -B—R 9 are independently phenyl, methoxy, ethoxy, trimethylpentyl or a group of formula (II):

wherein
R 1a , R 2a , R 3a , R 4a and R 5a are respectively as defined for R 1 , R 2 , R 3 , R 4 and R 5 .

14. The curable composition of claim 1 , wherein the phosphine oxide photoinitiator b) is selected from one of the following compounds:

15. The curable composition of claim 1 , wherein the composition comprises 0.05% to 10% by weight of phosphine oxide photoinitiator b) based on the total weight of the curable composition.

16. The curable composition of claim 1 , wherein the composition further comprises a cationically polymerizable compound.

17. The curable composition of claim 1 , wherein the composition further comprises a photoinitiator other than b) selected from the group consisting of benzoins, benzoin ethers, acetophenones, α-hydroxy acetophenones, benzyl, benzyl ketals, anthraquinones, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinones, polymeric derivatives thereof, a catio

Assignees

• Arkema France

Inventors

• Plenderleith Richard
• Klang Jeffrey
• Andersson Jonathan
• Ren Kangtai
• Wolf William
• Macneill Christopher

Classifications

• G03F7/029

  Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur · CPC title

• C08F222/22

  Esters containing nitrogen · CPC title

• B29K2105/16

  Fillers · CPC title

• B29K2033/00

  Use of polymers of unsaturated acids or derivatives thereof as moulding material {(B29K2035/00 takes precedence)} · CPC title

• B29C2035/0877

  using electron radiation, e.g. beta-rays · CPC title