Radiation-cured siloxane-modified-polyester coated article

Claim 2

An article of manufacture in accordance with claim 1 wherein said siloxane is an acyclic siloxane.

Claim 3

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof having an average depth of about 0.1 to about 4 mils, said coating comprising pigment and the in situ formed polymerization product of a film-forming solution of vinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said polyester having at least two carbon atoms of the principal carbon-to-carbon chain thereof separated by and connected to a divalent siloxane radical, said polyester being further characterized in that said siloxane comprises about 10 to about 60 weight percent of said polyester and said alpha-beta unsaturation of said polyester is limited to a concentration in the range of about 0.5 to about 3 units per 1,000 units molecular weight.

Claim 4

An article of manufacture in accordance with claim 4 wherein said siloxane is a cyclic siloxane containing about three to about 18 silicon atoms per molecule.

Claim 5

An article of manufacture in accordance with claim 4 wherein said siloxane is an acyclic siloxane containing about three to about 18 silicon atoms per molecule.

Claim 6

An article of manufacture in accordance with claim 4 wherein said vinyl monomers are a mixture of acrylic monomers and vinyl hydrocarbon monomers.

Claim 7

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising the in situ formed polymerization product of a film-forming solution of vinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said polyester being formed by first reacting a polyhydric alcohol and a siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and hydrocarbonoxy groups and subsequently reacting the resultant siloxane-containing reaction product with an alpha-beta olefinically unsaturated dicarboxylic acid or its anhydride and a second acid selected from the group consisting of dicarboxylic acids and tricarboxylic acids, the alpha-beta olefinic unsaturation of said polyester being provided solely by said alpha-beta olefinically unsaturated dicarboxylic acid with the relative proportions of said alpha-beta olefinically unsaturated dicarboxylic acid and said second acid being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 0.5 to about 5 units per 1, 000 units molecular weight, said siloxane comprising at least about 10 WEIGHT percent of said polyester.

Claim 8

An article of manufacture in accordance with claim 8 wherein said siloxane is a cyclic siloxane.

Claim 9

An article of manufacture in accordance with claim 8 wherein said siloxane is an acyclic siloxane.

Claim 10

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising pigment and the in situ formed polymerization product of a film-forming solution of vinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said vinyl monomers being selected from the group consisting of acrylic monomers and vinyl hydrocarbon monomers, said polyester having a molecular weight of at least about 1,000 and at least two carbon atoms of the principal carbon-to-carbon chain thereof separated by and connected to a siloxane, said polyester being formed by first reacting a monomeric diol with a siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and hydrocarbonoxy groups and containing at least three silicon atoms and subsequently reacting the resultant siloxane-containing reaction product with an alpha-beta olefinically unsaturated dicarboxylic acid or its anhydride and a second acid selected from the group consisting of dicarboxylic acids and tricarboxylic acids, the composition of said second acid being such that the alpha-beta olefinic unsaturation of said polyester is provided solely by said alpha-beta olefinically unsaturated dicarboxylic acid with the relative proportions of said alpha-beta olefinically unsaturated dicarboxylic acid and said second acid being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 0.5 to about 5 units per 1,000 units molecular weight, said siloxane comprising about 15 to about 50 weight percent of said polyester.

Claim 11

An article of manufacture in accordance with claim 11 wherein said siloxane containing about three to about 18 silicon atoms per molecule.

Claim 12

An article of manufacture in accordance with claim 11 wherein said siloxane is an acyclic siloxane containing about three to about 18 silicon atoms per molecule.

Claim 13

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising pigment and the in situ formed polymerization product of a film-forming solution of monovinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said polyester having a molecular weight of about 1,000 to about 20,000 and at least two carbon atoms of the principal carbon-to-carbon chain thereof separated by and connected to a siloxane, said polyester being formed by first reacting a diol with a siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and hydrocarbonoxy groups and containing about three to about 18 silicon atoms and subsequently reacting the resultant siloxane-containing reaction product with maleic anhydride and a second carboxylic acid component selected from the group consisting of dicarboxylic acids and tricarboxylic acids, the composition of said second acid being such that the alpha-beta olefinic unsaturation of said polyester is provided solely by said maleic anhydride with the relative proportions of said maleic anhydride and said second carboxylic acid component being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 0.5 to about 3 units per 1,000 units molecular weight, said siloxane comprising about 15 to about 50 weight percent of said polyester.

Claim 14

An article of manufacture coMprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising pigment and the in situ formed polymerization product of a film-forming solution of vinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said vinyl monomers being selected from the group consisting of acrylic monomers and vinyl hydrocarbon monomers, said polyester having a molecular weight of about 1,000 to about 20,000 and at least two carbon atoms of the principal carbon-to-carbon chain thereof separated by and connected to a siloxane, said polyester being formed by first reacting at least two molar parts of a diol with one part siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and hydrocarbonoxy groups and containing about three to about 18 silicon atoms and subsequently reacting the resultant siloxane-containing reaction product with an alpha-beta olefinically unsaturated dicarboxylic acid or its anhydride and a second acid selected from the group consisting of phthalic acid, tetrahydrophthalic acid, 1,2,4-benzene tricarboxylic acid and their anhydrides, the alpha-beta olefinic unsaturation of said polyester being provided solely by said alpha-beta olefinically unsaturated dicarboxylic acid with the relative proportions of said alpha-beta olefinically unsaturated dicarboxylic acid and said second acid being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 0.5 to about 3 per 1,000 units molecular weight, said siloxane comprising about 15 to about 60 weight percent of said polyester.

Claim 15

An article of manufacture in accordance with claim 15 wherein said dicarboxylic acid is maleic acid introduced in the form of its anhydride.

Claim 16

An article of manufacture in accordance with claim 15 wherein said second acid is tetrahydrophthalic acid introduced in the form of its anhydride.

Claim 17

An article of manufacture in accordance with claim 15 wherein said second acid is phthalic acid introduced in the form of its anhydride.

Claim 18

An article of manufacture in accordance with claim 15 wherein said acid is 1,2,4-benzene tricarboxylic acid introduced in the form of its anhydride.

Claim 19

An article of manufacture in accordance with claim 15 wherein said hydrocarbonoxy groups are C1 to C8 alkoxy groups.

Claim 20

An article of manufacture in accordance with claim 15 wherein said polyester contains about 1 to about 3 units of alpha-beta olefinic unsaturation per 1,000 units molecular weight.

Claim 21

An article of manufacture in accordance with claim 15 wherein said siloxane contains about six to about 12 silicon atoms per molecule.

Claim 22

An article of manufacture in accordance with claim 15 wherein said diol is a C2 to C10 diol.

Claim 23

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising the in situ formed polymerization product of a film-forming solution of vinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said vinyl monomers being selected from the group consisting of acrylic monomers and vinyl hydrocarbon monomers, said polyester having a molecular weight of about 1,000 to about 20,000 and at least two carbon atoms of the principal carbon-to-carbon chain thereof separated by and connected to a siloxane, said polyester being formed by first reacting neopentyl glycol with a siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and C1 to C8 alkoxy groups and containing about three to about 18 silicon atoms and subsequently reacting the resultant siloxane-containing reaction product with maleic anhydride and tetrahydrophthalic anhydride, the relative proportions of said maleic anhydride and said tetrahydrophthalic anhydride being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 1 to about 3 units per 1,000 units molecular weight, said siloxane comprising about 15 to about 50 weight percent of said polyester.

Claim 24

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising the in situ formed polymerization product of a film-forming solution of vinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said polyester being formed by first reacting a polyhydric alcohol, an alpha-beta olefinically unsaturated dicarboxylic acid or its anhydride and a second acid selected from the group consisting of dicarboxylic acids and tricarboxylic acids and subsequently reacting the resultant hydroxylated polymer with a siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and hydrocarbonoxy groups, the composition of said second acid being such that the alpha-beta olefinic unsaturation of said polyester is provided solely by said dicarboxylic acid with the relative proportions of said dicarboxylic acid and said second acid being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 0.5 to about 5 units per 1,000 units molecular weight, said siloxane comprising at least about 10 weight percent of said polyester.

Claim 25

An article of manufacture in accordance with claim 25 wherein said siloxane is cyclic siloxane.

Claim 26

An article of manufacture in accordance with claim 25 wherein said siloxane is an acyclic siloxane.

Claim 27

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising pigment and the in situ formed polymerization product of a film-forming solution of monovinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said polyester having a molecular weight of about 1,000 to about 20,000 and at least two carbon atoms of the principal carbon-to-carbon chain thereof separated by and connected to a siloxane, said polyester being formed by first reacting a diol, maleic anhydride and a second carboxylic acid component selected from the group consisting of dicarboxylic acids and tricarboxylic acids, and subsequently reacting the resultant hydroxylated polymer with a siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and hydrocarbonoxy groups, the composition of said second acid being such that the alpha-beta olefinic unsaturation of said polyester is provided solely by said maleic anhydride with the relative proportions of said maleic anhydride and said second acid being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 0.5 to about 3 units per 1, 000 units molecular weight, said siloxane comprising about 15 to about 50 weight percent of said polyester.

Claim 28

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising pigment and the in situ formed polymerization product of a film-forming solution of vinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said vinyl monomers being selected from the group consistIng of acrylic monomers and vinyl hydrocarbon monomers, said polyester having a molecular weight of about 1,000 to about 20,000 and at least two carbon atoms of the principal carbon-to-carbon chain thereof separated by and connected to a siloxane, said polyester being formed by first reacting a diol, an alpha-beta olefinically unsaturated dicarboxylic acid or its anhydride and a second acid selected from the group consisting of phthalic acid, tetrahydrophthalic acid, 1,2,4-benzene tricarboxylic acid and their anhydrides and subsequently reacting at least two molar parts of the resultant hydroxylated polymer with one molar part of a siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and hydrocarbonoxy groups, the alpha-beta olefinic unsaturation of said polyester being provided solely by said alpha-beta olefinically unsaturated dicarboxylic acid with the relative proportions of said alpha-beta olefinically unsaturated dicarboxylic acid and said second acid being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 0.5 to about 3 per 1,000 units molecular weight said siloxane comprising about 15 to about 60 weight percent of said polyester.

Claim 29

An article of manufacture in accordance with claim 29 wherein said dicarboxylic acid is maleic acid introduced in the form of its anhydride.

Claim 30

An article of manufacture in accordance with claim 29 wherein said second acid is tetrahydrophthalic acid introduced in the form of its anhydride.

Claim 31

An article of manufacture in accordance with claim 29 wherein said second acid is phthalic acid introduced in the form of its anhydride.

Claim 32

An article of manufacture in accordance with claim 29 wherein said acid is 1,2,4-benzene tricarboxylic acid introduced in the form of its anhydride.

Claim 33

An article of manufacture in accordance with claim 29 wherein said hydrocarbonoxy groups are C1 to C8 alkoxy groups.

Claim 34

An article of manufacture in accordance with claim 29 wherein said polyester contains about 1 to about 3 units of alpha-beta olefinic unsaturation per 1,000 units molecular weight.

Claim 35

An article of manufacture in accordance with claim 29 wherein said diol is a C2 to C10 diol.

Claim 36

An article of manufacture in accordance with claim 29 wherein said siloxane contains about six to about 12 silicon atoms per molecule.

Claim 37

An article of manufacture comprising a substrate and an adherent coating of paint on an external surface thereof, said coating comprising the in situ formed polymerization product of a film-forming solution of vinyl monomers and an alpha-beta olefinically unsaturated siloxane-modified polyester cross-linked on said surface by ionizing radiation with an electron beam, said vinyl monomers being selected from the group consisting of acrylic monomers and vinyl hydrocarbon monomers, said polyester having a molecular weight of about 1,000 to about 20,000 and at least two carbon atoms of the principal carbon-to-carbon chain thereof separated by and connected to a siloxane, said polyester being formed by first reacting neopentyl glycol, maleic anhydride, and tetrahydrophthalic anhydride and subsequently reacting the resultant hydroxylated polymer with a siloxane having in its molecular structure at least two functional groups selected from the group consisting of hydroxyl groups and C1 to C8 alkoxy groups and containing about three to about 18 silicon atoms, the relative proportions of said maleic anhydride and said tetrahydrophthalic anhydride being such as to limit the alpha-beta olefinic unsaturation units in said polyester to a concentration in the range of about 1 to about 3 units per 1,000 units molecular weight, said siloxane comprising about 15 to about 50 weight percent of said polyEster.