Polymerizable composition exhibiting permanent color change as cure indicator
View Patent ↗A polymerizable acrylate or epoxy composition includes a dye comprised of a conjugated system containing a chromophore that is subject to effective decoupling, by a reactive alkylating species generated by the polymerization initiator, to produce a permanent loss of color and thereby to indicate that curing has occurred.
1. A composition that cures by polymerization and that exhibits a substantially permanent color change during curing, comprised of: at least one polymerizable compound, the reaction of which is initiated by an active species selected from a first group, consisting of free radicals and ions; at least one initiator ingredient that generates said active initiating species when activated, said at least one initiator ingredient being present in an amount sufficient to effect substantially complete curing of said composition; and a non-photobleaching dye, present in said composition in an amount sufficient to impart perceptible color to said composition in the uncured state, the molecule of said dye comprising at least one conjugated system containing a chromophore that is subject to effective permanent decoupling, by reaction at at least one site, so as to cause substantially complete and substantially irreversible loss of said color, said composition containing at least one ingredient that produces a reactive alkylating species, that is effective for decoupling of said chromophore, in the presence of said active initiating species and under the conditions of polymerization of said composition.
2. The composition of claim 1 wherein said molecule of said dye comprises a plurality of conjugated systems interconnected by a linking region, said linking region providing said at least one reaction site.
3. The composition of claim 1 wherein said at least one polymerizable compound is a monofunctional unsaturated (meth)acrylate monomer, and said active initiating species constitutes free radicals.
4. The composition of claim 1 wherein said at least one polymerizable compound is an epoxy monomer, and wherein said active initiating species constitutes a cation.
5. The composition of claim 1 wherein said dye is a cationic triphenyl methane compound.
6. The composition of claim 5 wherein said dye is selected from the group consisting of Crystal Violet, Victoria Blue, Malachite Green and New Fuchsin.
7. The composition of claim 1 wherein said at least one initiator ingredient is a photoinitiator.
8. The composition of claim 7 wherein said at least one photoinitiator ingredient is responsive to actinic radiation in the UV range of wavelengths for generating said active initiating species.
9. The composition of claim 8 wherein said composition additionally includes a coagent that sensitizes said UV-responsive photoinitiator ingredient to respond to wavelengths in the visible range.
10. The composition of claim 3 wherein said composition additionally includes a vinyl compound copolymerizable with said (meth)acrylate monomer.
11. The composition of claim 4 wherein said composition additionally includes a vinyl compound copolymerizable with said epoxy monomer.
12. The composition of claim 1 wherein said dye is reacted with a polymerizable compound in said composition so as to become part of a growing polymer chain produced during curing of said composition.
13. A method for determining substantially complete cure of a polymerizable composition, including the steps:
providing a polymerizable composition comprising at least one polymerizable compound that is initiated by an active species selected from a first group, consisting of free radicals and ions; at least one initiator ingredient that generates said active initiating species when activated, said at least one initiator ingredient being present in an amount sufficient to effect substantially complete curing of said composition; and a non-photobleaching dye, present in said composition in an amount sufficient to impart perceptible color to said composition in the uncured state, the molecule of said dye comprising at least one conjugated system containing a chromophore that is subject to effective permanent decoupling, by reaction at at least one site, so as to cause substantially complete and substantially irreversible loss of said color, said composition containing at least one ingredient that produces a reactive alkylating species, that is effective for decoupling of said chromophore, in the presence of said active initiating species and under the conditions of polymerization of said composition;
subjecting said composition to conditions for effecting activation of said initiator ingredient to generate said active initiating species; and
monitoring said composition to detect the loss of said perceptible color imparted thereto by said non-photobleaching dye.
14. The method of claim 13 wherein said molecule of said dye comprises a plurality of conjugated systems interconnected by a linking region, said linking region providing said at least one reaction site.
15. The method of claim 13 wherein said at least one polymerizable compound is a monofunctional unsaturated (meth)acrylate monomer, and said active initiating constitutes free radicals.
16. The method of claim 13 wherein said at least one polymerizable compound is an epoxy monomer, and wherein said active initiating species constitutes a cation.
17. The method of claim 13 wherein said dye is a cationic triphenyl methane compound.
18. The method of claim 13 wherein said at least one initiator ingredient is a photoinitiator, and wherein said conditions for effecting activation comprise exposing said composition to actinic radiation.
19. The method of claim 18 wherein said at least one photoinitiator ingredient is responsive to actinic radiation in the UV range of wavelengths for generating said active initiating species, and wherein said conditions for effecting activation comprise exposing said composition to UV radiation.
20. The method of claim 18 wherein said at least one photoinitiator ingredient is responsive to actinic radiation in the UV range of wavelengths for generating said active initiating species, wherein said polymerizable composition additionally includes a coagent that sensitizes said UV-responsive photoinitiator ingredient to respond to wavelengths in the visible range, and wherein said conditions for effecting activation comprise exposing said composition to visible wavelengths of radiation.
21. The method of claim 15 wherein said composition additionally includes a vinyl compound copolymerizable with said (meth)acrylate monomer.
22. The method of claim 16 wherein said composition additionally includes a vinyl compound copolymerizable with said epoxy monomer.
23. A composition that cures by polymerization and that exhibits a permanent loss of color during curing, comprised of: at least one polymerizable monofunctional unsaturated (meth)acrylate monomer, the reaction of which is initiated by an active species consisting of free radicals; at least one initiator ingredient that generates said active initiating species when activated, said at least one initiator ingredient being present in an amount of about 1 to 8 weight percent, and sufficient to effect substantially complete curing of said composition; and a non-photobleaching dye, present in said composition in an amount sufficient to impart perceptible color to said composition in the uncured state, the molecule of said dye comprising at least one conjugated system containing a chromophore that is subject to effective permanent decoupling, by reaction at at least one site, so as to cause substantially complete and substantially irreversible loss of said color, said composition containing at least one ingredient that produces a reactive alkylating species, that is effective for decoupling of said chromophore, in the presence of said active initiating species and under the conditions of polymerization of said composition.