Radiation-curable coatings for plastic substrates from multifunctional acrylate oligomers

• US 7,232,540 B2
• Filed: 05/02/2004
• Issued: 06/19/2007
• Est. Priority Date: 05/02/2004
• Status: Expired due to Fees

• Current Assignee: Ashland Licensing and Intellectual Property Llc
• Original Assignee: Ashland Licensing and Intellectual Property Llc
• Inventors: Gould, Michael, Mejiritski, Alexandre, Marino, Thomas L., Martin, Dustin B., Sheridan, Matthew S.
• Primary Examiner(s): McClendon; Sanza L.
• Application Number:
  US10/836,747
• Publication Number:
  US 20050245631A1
• Time in Patent Office: 1,143 Days
• Field of Search: 522/71, 522/81, 522/173, 522/174, 522/178, 522/100, 522/104, 522/90, 522/96, 522/97, 522/181, 522/182, 522/183, 522/904, 428/411.1, 428/500, 264/446, 264/447, 264/448, 264/494, 264/495
• US Class Current: 264/494
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 265/06 Polymerisation of acrylate or methacrylate esters on to polymers thereof
• CPC Class Codes: C08F 283/01 on to unsaturated polyesters C08F283/004 takes precedence
• CPC Class Codes: C08F 289/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/061 Polyesters; Polycarbonates
• CPC Class Codes: C08J 2433/00 Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
• CPC Class Codes: C08J 7/0427 with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/043 Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/046 Forming abrasion-resistant coatings; Forming surface-hardening coatings
• CPC Class Codes: C08K 5/07 Aldehydes; Ketones
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C09D 133/062 Copolymers with monomers not covered by C09D133/06
• CPC Class Codes: C09D 133/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C09D 133/14 of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09D 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09D151/04, C09D151/06 take precedence
• CPC Class Codes: C09D 151/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 167/07 having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 175/16 having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: Y10S 522/904 Monomer or polymer contains initiating group
• CPC Class Codes: Y10T 428/31504 : Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31855 : Of addition polymer from unsaturated monomers

Abstract

The present invention relates to radiation-curable coating formulations specifically for plastic substrates. The present invention specifically relates to resinous Michael addition products of β-dicarbonyl compounds and Lewis-functional multifunctional acrylate esters. The present invention further relates to methods of fabricating and using the inventive compounds.

Claims

1. An article comprising a plastic substrate and a UV-curable Michael resin composition, wherein said UV-curable Michael resin composition comprises a resinous Michael addition product of a β

-dicarbonyl compound and a Lewis-functional multifunctional acrylate ester wherein said resin has a surface tension in the range of from about 30 to about 70 dynes/cm and wherein said plastic substrate is coated with said UV-curable Michael resin composition.

2. The article according to claim 1, wherein said Lewis-functional multifunctional acrylate ester comprises a chemical moiety selected from the group consisting of hydroxyl, epoxy, amine, acid, urethane, melamine, ether, ester and mixtures thereof.

3. The article according to claim 1, wherein said β

-dicarbonyl compound is selected from the group consisting of β

-keto esters, β

-diketones, β

-keto amides, β

-keto anilides and mixtures thereof.

4. The article according to claim 1, wherein said β

-dicarbonyl compound is selected from the group consisting of methyl acetoacetate, ethyl acetoacetate, 2-(methoxyethyl) acetoacetate, glycidyl acetoacetate, acetoacetanilide, 2,4-pentanedione and mixtures thereof.

5. The article according to claim 1, wherein said Lewis-functional multifunctional acrylate ester is selected from the group consisting of trimethylolpropane triacrylate, dipropylene glycol diacrylate, trifunctional acrylic s-triazine, hexanediol diacrylate, pentaerythritol triacrylate, propoxylated glycol acrylates and mixtures thereof.

6. The article according to claim 1, wherein sais UV-curable Michael resin composition further comprises at least one reactive monomer.

7. The article according to claim 1, wherein said UV-curable Michael resin composition further comprises at least one agent selected from the group consisting of flaw and leveling additives, wetting agents, deaerating agents, photoinitiators, matting agents, colloidal silica, pigments, dyes, adhesion promoters and mixtures thereof.

8. The article according to claim 1, wherein said plastic substrate is treated to raise the surface energy of said plastic substrate to above 35 dynes/cm prior to coating with said DV-curable Michael resin composition.

9. The article according to claim 1, wherein said UV-curable Michael resin composition is cured.

10. A method of coating a plastic substrate comprising:

providing a resin composition comprising a resinous Michael addition product of a β

-dicarbonyl compound and a Lewis-functional multifunctional acrylate ester wherein said uncrosslinked resin has a surface tension in the range of from about 30 to about 70 dynes/cm;

providing a plastic substrate;

optionally treating the said plastic substrate to raise the surface energy of said plastic substrate to above 35 dynes/cm;

applying said resin composition to said plastic substrate and

curing said resin composition.

11. The method according to claim 10, wherein said resin composition further comprises at least one agent selected from the group consisting of reactive diluent monomers, adhesion promoting monomers, flow and leveling additives, wetting agents, deaerating agents, photoinitiators, matting agents, colloidal silica, pigments, dyes, adhesion promoters and mixtures thereof.

12. The method according to claim 10, wherein said plastic substrate is treated to raise the surface energy of said plastic substrate to above 35 dynes/cm, and wherein said treatment is selected from the group consisting of corona discharge, flame, chromic acid etch, plasma, and application of primer coats.

13. The method according to claim 10, wherein applying said resin composition comprises a method selected from the group consisting of roll coating, spraying, brushing, and dip-coating.