Pressure-sensitive adhesives having improved adhesion to acid-rain resistant automotive paints

Claim 2

A pressure-sensitive adhesive consisting essentially of: a crosslinked copolymer of 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20° C.; (b) correspondingly, about 40 to about 10 parts by weight of a basic copolymerizable monomer having the formula ##STR7## wherein a represents an integer of 0 to 1; b represents an integer of 1; R is selected from the group consisting of H-- and CH 3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR8## wherein R 1 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle; R 2 is Selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle, wherein R 1 and R 2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 0 to about 3 parts by weight an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 0.05 to about 1 percent by weight of a crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.

Claim 3

The pressure-sensitive adhesive of claim 1 wherein the (meth)acrylate esters are selected from the group consisting of n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, 2-methyl butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isooctyl methacrylate, isononyl acrylate, isodecyl acrylate, and mixtures thereof.

Claim 4

The pressure-sensitive adhesive of claim 1 wherein the (meth)acrylate esters are selected from the group consisting of isooctyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof.

Claim 5

The pressure-sensitive adhesive of claim 1 wherein the moderately basic copolymerizable monomer is selected from the group consisting of N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl acrylamide, N,N-diethyl methacrylamide and mixtures thereof.

Claim 6

The pressure-sensitive adhesive of claim 1 wherein the acidic monomer is selected from the group consisting of ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphoric acids, and mixtures thereof.

Claim 7

The pressure-sensitive adhesive of claim 5 wherein the acidic monomer is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, beta-carboxyethyl acrylate, sulfoethyl methacrylate, and mixtures thereof.

Claim 8

The pressure-sensitive adhesive of claim 1 wherein the crosslinking agent is selected from the group consisting of multifunctional acrylates, substituted triazines, mono-ethylenically unsaturated aromatic ketones, mono-ethylenically unsaturated monoalkoxy silane compounds, dialkoxy silane compounds and trialkoxy silane compounds, and heat activated copolymerizable crosslinking agents.

Claim 9

A coated sheet material comprising a substrate having the pressure-sensitive adhesive of claim 1 coated thereon.

Claim 10

The coated sheet material of claim 8 wherein said substrate is selected from the group consisting of polyesters, polyvinylchloride, polypropylenes, polyurethanes, fluorinated ethylene-propylenes, polyacrylates, polyethylenes, neoprenes and silicones.

Claim 11

A double sided tape having the pressure-sensitive adhesive of claim 1 coated on at least one side.

Claim 12

A composite comprising a solid acidic surface coated with the adhesive of claim 1.

Claim 13

The composite of claim 1 wherein said solid acidic surface is selected from the group consisting of plastics, elastomers, and foams.

Claim 14

The composite of claim 11 wherein said solid acidic surface is polyvinylchloride.

Claim 15

The composite of claim 11 wherein said solid acidic surface is a paint coating.

Claim 16

The composite of claim 11 wherein said solid acidic surface is an automotive coating.

Claim 17

A composite comprising an article bonded to a solid acidic surface via the adhesive of claim 1.

Claim 18

The composite of claim 16 wherein said article is selected from the group consisting of emblems, moldings, decals, and films.

Claim 19

A pressure-sensitive adhesive consisting essentially of: a crosslinked copolymer comprising 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20° C.; (b) correspondingly, about 40 to about 10 parts by weight of a basic copolymerizable monomer having the formula ##STR9## wherein a represents an integer of 0 to 1; b represents an integer of 1; R is selected from the group consisting of H-- and CH 3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR10## wherein R 1 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle; R 2 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle, wherein R l and R 2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 1 to about 3 parts by weight of an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 1 to about 0.05 percent by weight of a crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.

Claim 20

A pressure-sensitive adhesive consisting essentially of: a crosslinked copolymer comprising 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20° C.; (b) correspondingly, about 40 to about 10 parts by weight of a basic copolymerizable monomer having the formula ##STR9## wherein a represents an integer of 0 to 1; b represents an integer of 1; R is selected from the group consisting of H-- and CH 3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR10## wherein R 1 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle; R 2 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle, wherein R l and R 2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 1 to about 3 parts by weight of an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 1 to about 0.05 percent by weight of a crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.

Claim 21

A composite comprising a solid acidic surface which is a paint coating coated with a pressure sensitive adhesive, the pressure sensitive adhesive consisting essentially of: a crosslinked copolymer of 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20° C.; (b) correspondingly, about 40 to about 10 parts by weight era basic copolymerizable monomer having the formula ##STR11## wherein a represents an integer of 0 to 1; b represents an integer of 1; R is selected from the group consisting of H-- and CH 3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR12## wherein R 1 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle; R 2 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle, wherein R 1 and R 2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 0 to about 3 parts by weight an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 0.05 to about 1 percent by weight of a crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.

Claim 22

A composite comprising a solid acidic surface which is a paint coating coated with a pressure sensitive adhesive, the pressure sensitive adhesive consisting essentially of: a crosslinked copolymer of 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20° C.; (b) correspondingly, about 40 to about 10 parts by weight era basic copolymerizable monomer having the formula ##STR11## wherein a represents an integer of 0 to 1; b represents an integer of 1; R is selected from the group consisting of H-- and CH 3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR12## wherein R 1 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle; R 2 is selected from the group consisting of an electron donating group and a radical which completes a ring structure including Y to form a heterocycle, wherein R 1 and R 2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 0 to about 3 parts by weight an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 0.05 to about 1 percent by weight of a crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.

Claim 23

A composite comprising a solid acidic surface which is an automotive coating coated with a pressure sensitive adhesive, the pressure sensitive adhesive consisting essentially of: a crosslinked copolymer of 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20° C.; (b) correspondingly, about 40 to about 10 parts by weight of a basic copolymerizable monomer having the formula ##STR13## wherein a represents an integer of 0 to 1; b represents an integer of 0 to 1; R is selected from the group consisting of H-- and CH 3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR14## wherein R 1 is selected from the group consisting of --H, an electron donating group, and a radical which completes a ring structure including Y to form a heterocycle; R 2 is selected from the group consisting of --H, an electron donating group, and a radical which completes a ring structure including Y to form a heterocycle, wherein R 1 and R 2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 0 to about 3 parts by weight an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 0.05 to about 1 percent by weight era crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.

Claim 24

A composite comprising a solid acidic surface which is an automotive coating coated with a pressure sensitive adhesive, the pressure sensitive adhesive consisting essentially of: a crosslinked copolymer of 100 parts by weight of monomer of elements (a), (b), and (c) wherein the copolymer comprises (a) about 60 to about 90 parts by weight of at least one monomer selected from the group consisting of monofunctional unsaturated (meth)acrylate esters of non-tertiary alkyl alcohols, and mixtures thereof, the alkyl groups of which comprise from about 4 to about 12 carbon atoms which as homopolymers have glass transition temperatures below about -20° C.; (b) correspondingly, about 40 to about 10 parts by weight of a basic copolymerizable monomer having the formula ##STR13## wherein a represents an integer of 0 to 1; b represents an integer of 0 to 1; R is selected from the group consisting of H-- and CH 3 --; X is selected from the group consisting of --O-- and --NH--; Y is a divalent linking group comprising 1 to 5 carbon atoms; Z is a non-sterically hindered group ##STR14## wherein R 1 is selected from the group consisting of --H, an electron donating group, and a radical which completes a ring structure including Y to form a heterocycle; R 2 is selected from the group consisting of --H, an electron donating group, and a radical which completes a ring structure including Y to form a heterocycle, wherein R 1 and R 2 cannot simultaneously represent a radical which completes a ring structure including Y to form a heterocycle; (c) about 0 to about 3 parts by weight an acidic monomer copolymerizable with the monomers of elements (a) and (b) wherein when the acidic monomer is included, the basic copolymerizable monomer should be present in a molar excess; (d) about 0.05 to about 1 percent by weight era crosslinking agent, based upon the total weight of (a) plus (b) plus (c); and (e) optionally a material selected from the group consisting of fillers, pigments, woven fabrics, nonwoven fabrics, foaming agents, antioxidants, stabilizers, fire retardants, viscosity adjusting agents, and solvents; wherein the pressure-sensitive adhesive has a basic character and wherein the pressure sensitive-adhesive has the ability to permanently bond to solid acidic surfaces.