Polycarbonate articles coated with an adherent, durable silica filled organopolysiloxane coating and process for producing same

Claim 2

A coated polycarbonate article having improved resistance to abrasion comprising a polycarbonate substrate coated with (i) an adhesion promoting primer layer comprising a photoreaction product of (a) at least one polyfunctional acrylic acid ester monomer; (b) at least one organo-silicon compound containing at least one organic group having olefinic unsaturation represented by the general formula R.sup.4.sub.c SiX.sub.4-c wherein c is an integer having a value from 1 to 3 inclusive, x is an alkoxy, acyloxy and aryloxy radical, and R 4 represents a radical selected from CH 2 ═CH--COO--R 5 --, CH 2 ═CCH 3 --COO--R 5 --, and ##STR45## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical; (c) at least one acrylate modified polymer; and (ii) a colloidal silica filled thermoset organopolysiloxane top coat disposed on said primer layer.

Claim 3

The article of claim 1 wherein said polyfunctional acrylic acid ester monomer is represented by the formula ##STR46## wherein n is an integer from 2 to 4 inclusive and R 1 is an n valent saturated aliphatic hydrocarbon radical, n valent substituted saturated aliphatic hydrocarbon radical, n valent olefinically unsaturated aliphatic hydrocarbon radical, n valent substituted olefinically unsaturated aliphatic hydrocarbon radical, n valent ether radical, n valent substituted ether radical, n valent polyether radical, n valent substituted polyether radical, n valent aromatic hydrocarbon radical, and n valent substituted aromatic hydrocarbon radical.

Claim 4

The article of claim 2 wherein R 1 is an n valent saturated aliphatic hydrocarbon radical, n valent olefinically unsaturated aliphatic hydrocarbon radical, n valent ether radical, n valent polyether radical, and n valent aromatic hydrocarbon radical.

Claim 5

The article of claim 3 wherein R 1 is an n valent saturated aliphatic hydrocarbon radical, n valent ether radical, and n valent polyether radical.

Claim 6

The article of claim 4 wherein R 4 represents a radical having the formula ##STR47## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 7

The article of claim 4 wherein R 4 represents a radical having the formula ##STR48## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 8

The article of claim 4 wherein R 4 represents a radical having the formula ##STR49## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 9

The article of claim 5 wherein X is an alkoxy radical and c is 1.

Claim 10

The article of claim 8 wherein said alkoxy radical is an ethoxy radical.

Claim 11

The article of claim 8 wherein said alkoxy radical is a methoxy radical.

Claim 12

The article of claim 6 wherein X is an alkoxy radical and c is 1.

Claim 13

The article of claim 11 wherein said alkoxy radical is an ethoxy radical.

Claim 14

The article of claim 11 wherein said alkoxy radical is a methoxy radical.

Claim 15

The article of claim 7 wherein X is an alkoxy radical and c is 1.

Claim 16

The article of claim 14 wherein said alkoxy radical is a methoxy radical.

Claim 17

The article of claim 14 wherein said alkoxy radical is an ethoxy radical.

Claim 18

The article of claim 1 wherein said acrylate modified polymer is selected from the group consisting of acrylate polyurethanes, acrylate alkyd polyurethanes, acrylate polycaprolactones, acrylate unsaturated acid modified drying oils, acrylate polyesters, and acrylate polyethers.

Claim 19

The article of claim 1 wherein said primer layer further contains the photoreaction products of resorcinol monobenzoate, alkyl substituted resorcinol monobenzoate, or mixtures thereof.

Claim 20

The article of claim 1 wherein said thermoset organopolysiloxane is a condensation product of a silanol having the formula R 6 Si(OH) 3 , wherein R 6 is an alkyl radical of from 1 to 3 carbon atoms, the vinyl radical, the 3,3,3-trifluoropropyl radical, the gamma-glycidoxypropyl radical and the gamma-methacryloxypropyl radical, at least 70 weight percent of the silanol being CH 3 Si(OH) 3 .

Claim 21

The article of claim 19 wherein said thermoset organopolysiloxane is the condensation product of CH 3 Si(OH) 3 .

Claim 22

The article of claim 19 wherein said top coat contains from about 10 to about 70 weight percent of colloidal silica and from about 30 to about 90 weight percent of the condensation product of said silanol.

Claim 23

A coated polycarbonate article having improved scratch, mar, abrasion and chemical solvent resistance comprising a polycarbonate substrate having deposited on the surface thereof (i) an ultraviolet radiation cured primer layer, said cured primer layer being the photoreaction product of a primer composition containing at least one polyfunctional acrylic acid ester monomer, at least one acrylate modified polymer, at least one organo-silicon compound containing at least one organic group having olefinic unsaturation, a photoinitiator, and a compound selected from resorcinol monobenzoate, lower alkyl substituted resorcinol monobenzoate, or mixtures thereof; and (ii) a cured colloidal silica filled thermoset organopolysiloxane top coat on said cured primer layer said top coat being the thermally cured product of a top coat composition comprising a dispersion of colloidal silica in a lower aliphatic alcohol-water solution of the partial condensate of a silanol of the formula RSi(OH) 3 wherein R is selected from alkyl radicals containing 1 to 3 carbon atoms, the vinyl radical, the 3,3,3-trifluoropropyl radical, the gamma-glycidoxypropyl radical and the gamma-methacryloxypropyl radical, at least 70 weight percent of the silanol being CH 3 Si(OH) 3 , said composition containing sufficient acid to provide a pH in the range of 3.0 to 6.0.

Claim 24

A coated polycarbonate article having improved scratch, mar, abrasion and chemical solvent resistance comprising a polycarbonate substrate having deposited on the surface thereof (i) an ultraviolet radiation cured primer layer, said cured primer layer being the photoreaction product of a primer composition containing at least one polyfunctional acrylic acid ester monomer, at least one acrylate modified polymer, at least one organo-silicon compound containing at least one organic group having olefinic unsaturation, a photoinitiator, and a compound selected from resorcinol monobenzoate, lower alkyl substituted resorcinol monobenzoate, or mixtures thereof; and (ii) a cured colloidal silica filled thermoset organopolysiloxane top coat on said cured primer layer said top coat being the thermally cured product of a top coat composition comprising a dispersion of colloidal silica in a lower aliphatic alcohol-water solution of the partial condensate of a silanol of the formula RSi(OH) 3 wherein R is selected from alkyl radicals containing 1 to 3 carbon atoms, the vinyl radical, the 3,3,3-trifluoropropyl radical, the gamma-glycidoxypropyl radical and the gamma-methacryloxypropyl radical, at least 70 weight percent of the silanol being CH 3 Si(OH) 3 , said composition containing sufficient acid to provide a pH in the range of 3.0 to 6.0.

Claim 25

The article of claim 22 wherein said organo-silicon compound is represented by the general formula R.sup.4.sub.c SiX.sub.4-c wherein c is an integer from 1 to 3 inclusive, X is an alkoxy, acyloxy, or aryloxy radical, and R 4 represents a radical selected from ##STR50## or ##STR51## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical; and (iv) an ultraviolet light photoinitiator.

Claim 26

The article of claim 23 wherein R 4 represents a radical having the formula ##STR52## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 27

The article of claim 23 wherein R 4 represents a radical having the formula ##STR53## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 28

The article of claim 23 wherein R 4 represents a radical having the formula ##STR54## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 29

The article of claim 24 wherein X is an alkoxy radical and c is 1.

Claim 30

The article of claim 27 wherein said alkoxy radical is a lower alkoxy radical.

Claim 31

The article of claim 25 wherein X is an alkoxy radical and c is 1.

Claim 32

The article of claim 29 wherein said alkoxy radical is a lower alkoxy radical.

Claim 33

The article of claim 26 wherein X is an alkoxy radical and c is 1.

Claim 34

The article of claim 31 wherein said alkoxy radical is a lower alkoxy radical.

Claim 35

The article of claim 22 wherein said polyfunctional acrylic acid ester monomer is represented by the formula ##STR55## wherein n is an integer from 2 to 4 inclusive and R 1 is an n valent saturated aliphatic hydrocarbon radical, n valent substituted saturated aliphatic hydrocarbon radical, n valent olefinically unsaturated aliphatic hydrocarbon radical, n valent substituted olefinically unsaturated aliphatic hydrocarbon radical, n valent ether radical, n valent substituted ether radical, n valent polyether radical, n valent substituted polyether radical, n valent aromatic hydrocarbon radical, and n valent substituted aromatic hydrocarbon radical.

Claim 36

The article of claim 33 wherein R 1 is an n valent saturated aliphatic hydrocarbon radical, n valent olefinically unsaturated aliphatic hydrocarbon radical, n valent ether radical, n valent polyether radical, and n valent aromatic hydrocarbon radical.

Claim 37

The article of claim 34 wherein R 1 is an n valent saturated aliphatic hydrocarbon radical, n valent ether radical, and n valent polyether radical.

Claim 38

The article of claim 22 wherein said acrylate modified polymer is selected from the group consisting of acrylate polyurethanes, acrylate alkyd polyurethanes, acrylate polycaprolactones, acrylate unsaturated acid modified drying oils, acrylate polyesters, and acrylate polyethers.

Claim 39

A process for producing a mar, abrasion, scratch and chemical solvent resistant coated polycarbonate article comprising the steps of: (i) applying onto the surface of a polycarbonate substrate an ultraviolet radiation curable primer composition containing (a) at least one polyfunctional acrylic acid ester monomer, (b) at least one organo-silicon compound containing at least one organic group having olefinic unsaturation, (c) resorcinol monobenzoate, alkyl substituted resorcinol monobenzoate, or mixtures thereof, (d) a photoinitiator, and (e) at least one acrylate modified polymer; (ii) curing said primer composition by exposing said primer composition to ultraviolet radiation to form a cured primer layer; (iii) applying onto said cured primer layer a silica filled further curable organopolysiloxane top coat composition comprising a dispersion of colloidal silica in a lower aliphatic-water solution of the partial condensate of a silanol of the formula R 6 Si(OH) 3 wherein R 6 is an alkyl radical containing 1 to 3 carbon atoms, the vinyl radical, the 3,3,3-trifluoropropyl radical, the gamma-glycidoxypropyl radical and the gamma-methacryloxypropyl radical, at least 70 weight percent of said silanol being CH 3 Si(OH) 3 , said composition containing sufficient acid to provide a pH in the range of 3.0 to 6.0; (iv) evaporating the volatile solvents from said top coat composition; and (v) applying heat to said composition to cure said top coat composition, whereby said silanol is condensed further to a silsesquioxane.

Claim 40

A process for producing a mar, abrasion, scratch and chemical solvent resistant coated polycarbonate article comprising the steps of: (i) applying onto the surface of a polycarbonate substrate an ultraviolet radiation curable primer composition containing (a) at least one polyfunctional acrylic acid ester monomer, (b) at least one organo-silicon compound containing at least one organic group having olefinic unsaturation, (c) resorcinol monobenzoate, alkyl substituted resorcinol monobenzoate, or mixtures thereof, (d) a photoinitiator, and (e) at least one acrylate modified polymer; (ii) curing said primer composition by exposing said primer composition to ultraviolet radiation to form a cured primer layer; (iii) applying onto said cured primer layer a silica filled further curable organopolysiloxane top coat composition comprising a dispersion of colloidal silica in a lower aliphatic-water solution of the partial condensate of a silanol of the formula R 6 Si(OH) 3 wherein R 6 is an alkyl radical containing 1 to 3 carbon atoms, the vinyl radical, the 3,3,3-trifluoropropyl radical, the gamma-glycidoxypropyl radical and the gamma-methacryloxypropyl radical, at least 70 weight percent of said silanol being CH 3 Si(OH) 3 , said composition containing sufficient acid to provide a pH in the range of 3.0 to 6.0; (iv) evaporating the volatile solvents from said top coat composition; and (v) applying heat to said composition to cure said top coat composition, whereby said silanol is condensed further to a silsesquioxane.

Claim 41

The process of claim 37 wherein said polyfunctional acrylic acid ester monomer is represented by the formula ##STR56## wherein n is an integer from 2 to 4 inclusive and R 1 is an n valent saturated aliphatic hydrocarbon radical, n valent substituted saturated aliphatic hydrocarbon radical, n valent olefinically unsaturated aliphatic hydrocarbon radical, n valent substituted olefinically unsaturated aliphatic hydrocarbon radical, n valent ether radical, n valent substituted ether radical, n valent polyether radical, n valent substituted polyether radical, n valent aromatic hydrocarbon radical, and n valent substituted aromatic hydrocarbon radical.

Claim 42

The process of claim 38 wherein R 1 is a n valent saturated aliphatic hydrocarbon radical, n valent olefinically unsaturated aliphatic hydrocarbon radical, n valent ether radical, n valent polyether radical, and n valent aromatic hydrocarbon radical.

Claim 43

The process of claim 39 wherein R 1 is a n valent saturated aliphatic hydrocarbon radical, n valent ether radical, and n valent polyether radical.

Claim 44

The process of claim 37 wherein said organo-silicon compound is represented by the general formula R.sup.4.sub.c SiX.sub.4-c wherein c is an integer from 1 to 3 inclusive, X is an alkoxy, acyloxy, or aryloxy radical, and R 4 is a compound represented by the formula ##STR57## and ##STR58## wherein Y is a hydrogen or methyl, and R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 45

The process of claim 41 wherein R 4 is a compound represented by the formula CH.sub.2 ═CH--COO--R.sup.5 -- wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 46

The process of claim 41 wherein R 4 is a compound represented by the formula ##STR59## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 47

The process of claim 41 wherein R 4 is a compound represented by the formula ##STR60## wherein R 5 is a divalent saturated aliphatic hydrocarbon radical.

Claim 48

The process of claim 42 wherein X is an alkoxy radical and c is 1.

Claim 49

The process of claim 43 wherein X is an alkoxy radical and c is 1.

Claim 50

The process of claim 44 wherein X is an alkoxy radical and c is 1.

Claim 51

The process of claim 37 wherein said acrylate modified polymer is selected from the group consisting of acrylate polyurethanes, acrylate alkyd urethane polymers, acrylate polycaprolactones, acrylate unsaturated acid modified drying oils, acrylate polyesters and acrylate polyethers.

Claim 52

A polycarbonate article having improved scratch, mar, abrasion and chemical solvent resistance comprising a polycarbonate substrate having disposed on the surface thereof (i) an ultraviolet radiation cured primer layer, said cured primer layer containing the photoreaction product of (a) at least one polyfunctional acrylic acid ester monomer, (b) at least one acrylate modified polymer, and (c) at least one organic silicon compound represented by the general formula R.sup.4.sub.c SiX.sub.4-c wherein c is an integer having a value from 1 to 3 inclusive, X is an alkoxy, acyloxy and aryloxy radical, and R 4 represents a radical selected from CH 2 ═CH--COO--R 5 --, CH 2 ═C(CH 3 )--COO--R 5 --, and ##STR61## wherein R 5 represents a divalent saturated aliphatic hydrocarbon radical; and (ii) a cured colloidal silica filled thermoset organopolysiloxane top coat disposed on said cured primer layer, said top coat being the thermally cured product of a top coat composition comprising a dispersion of colloidal silica in a lower aliphatic alcohol-water solution of the partial condensate of a silanol of the formula R 6 Si(OH) 3 wherein R 6 is selected from alkyl radicals containing 1 to 3 carbon atoms, the vinyl radical, the 3,3,3-trifluoropropyl radical, the gamma-glycidoxypropyl radical and the gamma-methacryloxypropyl radical, at least 70 weight percent of the silanol being CH 3 Si(OH) 3 , said composition containing sufficient acid to provide a pH in the range of 3.0 to 6.0.

Claim 53

A polycarbonate article having improved scratch, mar, abrasion and chemical solvent resistance comprising a polycarbonate substrate having disposed on the surface thereof (i) an ultraviolet radiation cured primer layer, said cured primer layer containing the photoreaction product of (a) at least one polyfunctional acrylic acid ester monomer, (b) at least one acrylate modified polymer, and (c) at least one organic silicon compound represented by the general formula R.sup.4.sub.c SiX.sub.4-c wherein c is an integer having a value from 1 to 3 inclusive, X is an alkoxy, acyloxy and aryloxy radical, and R 4 represents a radical selected from CH 2 ═CH--COO--R 5 --, CH 2 ═C(CH 3 )--COO--R 5 --, and ##STR61## wherein R 5 represents a divalent saturated aliphatic hydrocarbon radical; and (ii) a cured colloidal silica filled thermoset organopolysiloxane top coat disposed on said cured primer layer, said top coat being the thermally cured product of a top coat composition comprising a dispersion of colloidal silica in a lower aliphatic alcohol-water solution of the partial condensate of a silanol of the formula R 6 Si(OH) 3 wherein R 6 is selected from alkyl radicals containing 1 to 3 carbon atoms, the vinyl radical, the 3,3,3-trifluoropropyl radical, the gamma-glycidoxypropyl radical and the gamma-methacryloxypropyl radical, at least 70 weight percent of the silanol being CH 3 Si(OH) 3 , said composition containing sufficient acid to provide a pH in the range of 3.0 to 6.0.

Claim 54

The article of claim 49 wherein said cured primer contains a photoinitiator.

Claim 55

The article of claim 50 wherein said cured primer further contains the photoreaction products of resorcinol monobenzoate, lower alkyl substituted resorcinol monobenzoate, or mixtures thereof.

Claim 56

The article of claim 51 wherein said polyfunctional acrylic acid ester monomer is represented by the general formula (H.sub.2 C═CH--COO).sub.n R.sup.1 wherein n is an integer having a value from 2 to 4, and R 1 is a n valent saturated aliphatic hydrocarbon radical, n valent ether radical, and n valent polyether radical.

Claim 57

The article of claim 52 wherein R 4 is represented by the general formula CH.sub.2 ═CH--COO--R.sup.5 --.

Claim 58

The article of claim 52 wherein R 4 is represented by the general formula ##STR62##

Claim 59

The article of claim 53 wherein R 4 is represented by the general formula ##STR63##