Energy curable compositions having improved cure speeds

Claim 2

A polymerizable composition comprising a polymeric precursor as disclosed in (1) or (2) wherein (1) comprises at least one polyisocyanate, and at least one compound bearing at least two isocyanate-reactive hydrogen atoms, the isocyanate and reactive hydrogen-containing compound constituting polyurethane precursors, or (2) comprises at least one ethylenically-unsaturated monomer, at least one polyisocyanate, and at least one compound bearing at least two isocyanate-reactive hydrogen atoms, the isocyanate and reactive hydrogen-containing compound constituting polyurethane precursors, and a two-component curing agent for (1) or (2) comprising an ionic salt of an organometallic complex cation comprising at least one transition metal atom and at least one carbon to metal atom bond, and a peroxide selected from the group consisting of hydroperoxides and acyl peroxides, wherein said polymerizable composition, when subjected to sufficient energy to effect polymerization, provides a tack-free cured composition.

Claim 3

The composition according to claim 1 wherein said peroxide has the formula ##STR8## wherein R 1 and R 2 independently represent hydrogen or an organic group selected from the class consisting of (1) straight chain or branched aliphatic hydrocarbon group containing 1 to 50 carbon atoms and zero to 20 heteroatoms, (2) cycloaliphatic hydrocarbon group containing 2 to 50 carbon atoms and zero to 20 heteroatoms, (3) aromatic hydrocarbon group or heterocyclic aromatic group containing 3 to 15 carbon atoms and zero to 10 heteroatoms, (4) araliphatic hydrocarbon group containing 6 to 50 carbon atoms and zero to 20 heteroatoms, or (5) alkoxy groups having 1 to 50 carbon atoms and zero to 20 heteroatoms; wherein the heteroatoms that are present in R 1 and R 2 are those that do not interfere with the overall efficacy of the composition, m and n independently are 0 or 1, and w is an integer in the range of 1 to 4, with the provisos that when both R 1 and R 2 are an organic group, then m+n is equal to 1 or 2, and when R 1 is alkoxy, m=1, and when R 2 is alkoxy, n=1.

Claim 4

The composition according to claim 1 which is at least one of photopolymerizable, accelerated particle polymerizable, and thermally polymerizable.

Claim 5

The composition according to claim 1 wherein said ionic salt of an organometallic complex cation is an organometallic iron salt.

Claim 6

The composition according to claim 4 wherein said salt is present in an amount in the range of 0.01 to 20 weight percent of said polymeric precursors.

Claim 7

The composition according to claim 1 wherein said peroxide is present in an amount in the range of 0.01 to 20 weight percent of said polymeric precursor.

Claim 8

The composition according to claim 1 which has been subjected to sufficient energy to effect polymerization and provide a cured composition.

Claim 9

The composition according to claim 1 wherein said polyurethane precursor is at least one polyisocyanate and at least one polyol.

Claim 10

The composition according to claim 1 wherein said polyisocyanate has the formula Q(NCO).sub.p wherein p=an integer in the range of 2 to 4 and Q=represents an aliphatic hydrocarbon radical containing from 2 to 100 carbon atoms, and zero to 50 heteroatoms, a cycloaliphatic hydrocarbon radical containing from 4 to 100 carbon atoms and zero to 50 heteroatoms, an aromatic hydrocarbon radical or heterocyclic aromatic radical containing from 6 to 15 carbon atoms and zero to 10 heteroatoms, or an araliphatic hydrocarbon radical containing from 8 to 100 carbon atoms and zero to 50 heteroatoms, wherein the heteroatoms in all of the radicals are selected from the group consisting of non-peroxidic oxygen, sulfur, non-amino nitrogen, halogen, silicon, and non-phosphino phosphorus.

Claim 11

The composition according to claim 1 wherein said ethylenically-unsaturated monomer is selected from the group consisting of at least one of mono- or polyfunctional (meth)acrylates, (meth)acrylamides, vinyl compounds, allyl compounds, allyl ether compounds, and bireactive monomers containing a free radically polymerizable group and one of an isocyanate and an isocyanate reactive group.

Claim 12

The composition according to claim 10 wherein the weight ratio of said mono- and polyfunctional acrylates are in the range of 0.1:99.9 to 99.9:0.1.

Claim 13

The composition according to claim 1 wherein said ionic salt of an organometallic complex cation has the formula: [((L.sup.1)(L.sup.2)M).sub.b (L.sup.3)(L.sup.4)].sup.+e X.sub.fIII wherein M represents the same or different metals selected from the elements of Periodic Groups 4 to 10, with the proviso that Formula III can represent an organometallic salt having a mono- or bimetallic cation; L 1 represents none, 1, 2, or 3 ligands contributing pi-electrons that can be the same or different ligand selected from substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of contributing two to twelve pi-electrons to the valence shell of M; L 2 represents none or 1 to 6 ligands contributing an even number of sigma-electrons that can be the same or different selected from mono-, di-, and tri-dentate ligands, each contributing 2, 4, or 6 sigma-electrons to the valence shell of M; L 3 represents none, 1 or 2 bridging ligands pi-electrons that can be the same or different ligand selected from substituted or unsubstituted acyclic and cyclic unsaturated compounds and groups and substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of acting as a bridging ligand contributing 2 to 24 pi-electrons to the valence shells of two metal atoms simultaneously; L 4 represents none, 1, 2 or 3 bridging ligands contributing an even number of sigma-electrons that can be the same or different selected from mono, di, and tri-dentate ligands, each donating 2, 4, or 6 sigma-electrons to the valence shells of two M simultaneously; with the proviso that the total electronic charge contributed to M by the ligands L 1 , L 2 , L 3 and L 4 plus the product of ionic charge on M with b results in a residual net positive charge of e to the cation; b is an integer having a value of 1 or 2; e is an integer having a value of 1 or 2, the residual electrical charge of the cation; X is an anion selected from organic sulfonate anions and halogen-containing complex anions of a metal or metalloid; f is an integer of 1 or 2, the number of anions required to neutralize the charge e on the cation.

Claim 14

The composition according to claim 1 wherein said peroxide is a hydroperoxide.

Claim 15

The composition according to claim 1 wherein said peroxide is an acyl peroxide.

Claim 16

The composition according to claim 1 which is a paint.

Claim 17

The composition according to claim 1 further comprising an effective amount of a photosensitizer.

Claim 18

A coated article comprising the cured composition according to claim 7.

Claim 19

A layered structure comprising a substrate having coated on at least one surface thereof the polymerizable composition according to claim 1.

Claim 22

The method according to claim 19 wherein said energy is at least one of electromagnetic radiation, accelerated particles, or thermal energy.

Claim 23

The method according to claim 19 wherein polymerization is effected in two stages, the first stage involving radiation and the second step involving thermal cure.

Claim 24

The method according to claim 19 wherein said two-component curing agent is present in the range of 0.02 to 25 weight percent of said polymeric precursors.

Claim 25

A kit for preparing a latently curable composition according to claim 1 to provide a paint and being a two package kit, said packages being capable of being mixed when the composition is to be applied, said kit comprising the combination of first and second packages wherein said isocyanate reactive hydrogen-containing compound and said polyisocyanate are in separate packages.

Claim 26

The kit according to claim 23 wherein said first package comprises a mixture of isocyanate reactive hydrogen-containing compound, free-radically polymerizable compound, and said effective amount of said organometallic salt, and said second package comprises a mixture of polyisocyanate and an effective amount of said peroxide of the invention.

Claim 27

The kit according to claim 23 wherein said first package comprises a mixture of isocyanate reactive hydrogen-containing compound and an effective amount of said peroxide of the invention, and said second package comprises a mixture of polyisocyanate and free-radically polymerizable compound and an effective amount of said organometallic salt.

Claim 28

The kit according to claim 23 wherein said kit comprises: in one package, isocyanate reactive hydrogen-containing compound, free-radically polymerizable compound, pigment, adjuvants, oxygen scavenger, an effective amount of said organometallic salt, and optionally solvents; and in a second package, polyisocyanate, an effective amount of said peroxide of the invention, and optionally solvents.