Stabilizer for thiol-ene compositions

Patent metadata

Field	Value
Publication number	US-10995270-B2
Application number	US-202016737106-A
Country	US
Kind code	B2
Filing date	Jan 8, 2020
Priority date	Dec 2, 2013
Publication date	May 4, 2021
Grant date	May 4, 2021

Abstract

The present invention relates to stabilizers for thiol-ene compositions and to radiation curable thiol-ene compositions based thereon. Such radiation curable compositions can advantageously be used in inks, overprint varnishes, coatings, adhesives, for the making of 3D objects and for the making of solder resist and gel nails. Provided in particular is an inhibitor system (I) for thiol-ene compositions based on —at least one inhibitor compound (i) having a % DPPH radical scavenging activity of at least 90%, the inhibitor compound (i) being selected from substituted benzene compounds or substituted naphthalene compounds containing at least two substituents selected from the group consisting of hydroxyl groups and C1-C3 alkoxy groups bonded directly to the benzene or the naphthalene ring, —at least one acidic compound (ii) having a pKa between 1 and 3, and —at least one compound (iii) selected from the group consisting of phosphites and phosphonites, with the proviso that if the inhibitor compound (i) is a substituted benzene that it contains at least two hydroxyl groups bonded directly to the benzene ring. Also provided is an inhibitor system (II) for thiol-ene compositions based on that is based on —at least one inhibitor compound (i) having a % DPPH radical scavenging activity of at least 90%, the inhibitor compound (i) being selected from substituted benzene compounds or substituted naphthalene compounds containing at least two substituents selected from the group consisting of hydroxyl groups and C1-C3 alkoxy groups bonded directly to the benzene or the naphthalene ring, —at least one compound (iv) selected from the group consisting of spirophosphites, and —optionally, at least one acidic compound (ii) having a pKa between 1 and 3, and with the proviso that if the inhibitor compound (i) is a substituted benzene that it contains at least two hydroxyl groups bonded directly to the benzene ring.

First claim

The invention claimed is:

1. An inhibitor system (II) for thiol-ene compositions based on
at least one inhibitor compound (i) having a % 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity of at least 90%, the inhibitor compound (i) being selected from substituted benzene compounds or substituted naphthalene compounds containing at least two substituents selected from the group consisting of hydroxyl groups and C1-C3 alkoxy groups bonded directly to the benzene or the naphthalene ring,
at least one compound (iv) selected from the group consisting of spirophosphites, and
optionally, at least one acidic compound (ii) having a pKa between 1 and 3, and with the proviso that if the inhibitor compound (i) is a substituted benzene that it contains at least two hydroxyl groups bonded directly to the benzene ring.

2. The inhibitor system according to claim 1 , wherein the at least one inhibitor compound (i) is selected from the group consisting of (ia) substituted benzenes containing at least two hydroxyl groups bonded directly to the benzene ring and (iib) substituted naphthalenes containing at least one hydroxyl and at least one methoxy group bonded directly to the naphthalene ring.

3. The inhibitor system according to claim 1 , wherein the at least one inhibitor compound (i) is selected from the group consisting of 4-methoxy-1-naphthol, catechol, tert-butyl catechol, hydroquinone, gallic acid, the esters of gallic acid, pyrogallol and 2,4,5-trihydroxybutyrophenone.

4. The inhibitor system according to claim 1 , wherein the at least one inhibitor compound (i) is selected from 4-methoxy-1-naphthol and/or from the esters of gallic acid.

5. The inhibitor system according to claim 1 , wherein the acidic compound (ii) is selected from oxalic acid and/or from the esters of phosphoric acid.

6. A method for stabilizing thiol (meth)acrylate compositions comprising adding the inhibitor system (II) of claim 1 to a thiol (meth)acrylate composition.

7. A radiation curable thiol (meth)acrylate composition (III) comprising at least one inhibitor system according to claim 1 , at least one thiol compound (v), and further at least one (meth)acrylated compound (vi).

8. The radiation curable thiol (meth)acrylate composition of claim 7 , wherein the at least one thiol compound (v) comprises at least three thiol groups.

9. The radiation curable thiol (meth)acrylate composition of claim 7 , wherein the at least one thiol compound (v) is selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutylate), trimethylolpropane tris (3-mercaptopropionate) and trimethylolpropane tris (3-mercaptobutylate).

10. The radiation curable thiol (meth)acrylate composition of claim 7 , wherein the (meth)acrylated compound is selected from (poly)urethane (meth)acrylates, (poly)ester (meth)acrylates, (poly)ether (meth)acrylates, epoxy (meth)acrylates and/or (meth)acrylated (meth)acrylics.

11. The radiation curable thiol (meth)acrylate composition of claim 7 comprising from 10 ppm to 5% by weight of compounds (i), from 10 ppm to 30% by weight of compounds (ii), from 1 to 70% by weight of compounds (v) and from 30 to 99% by weight of compounds (vi).

12. The radiation curable composition of claim 7 , wherein the ratio of compounds (vi) to compounds (v) is from 95:5 to 30:70.

13. A method of making inks, overprint varnishes, coating compositions, adhesives, 3D objects, solder resist, and gel nails comprising adding the radiation curable thiol (meth)acrylate composition (III) of claim 7 to at least one of inks, overprint varnishes, coating compositions, adhesives, 3D objects, solder resist, and gel nails.

Assignees

• ALLNEX Belgium SA

Inventors

• Boogaerts Luc
• Cappelle Steven
• Van Den Bergen Hugues

Classifications

• C08F20/38

  Esters containing sulfur · CPC title

• C08K5/0008 Primary

  Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59 · CPC title

• C07C271/22

  to carbon atoms of hydrocarbon radicals substituted by carboxyl groups · CPC title

• C08K5/49

  Phosphorus-containing compounds {(C08K5/0091 takes precedence)} · CPC title

• C09K15/06

  containing oxygen · CPC title