Radiation curing of prepolymer coating compositions

• US 4,303,696 A
• Filed: 08/11/1980
• Issued: 12/01/1981
• Est. Priority Date: 05/07/1975
• Status: Expired due to Term

• Current Assignee: Design Rite LLC
• Original Assignee: Design Rite LLC
• Inventors: Brack, Karl
• Primary Examiner(s): Morgenstern, Norman
• Assistant Examiner(s): Page, Thurman K.
• Application Number:
  US06/177,001
• Time in Patent Office: 477 Days
• Field of Search: 204/159.14, 204/159.19, 204/159.22, 204/159.23, 204/159.24, 204/159.13, 260/28, 260/33.60 B, 260/28.5 R, 427/44, 427/54.1
• US Class Current: 427/503
• CPC Class Codes: B41M 7/0045 using protective coatings or film forming compositions cured by mechanical wave energy, e.g. ultrasonics, cured by electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams, or cured by magnetic or electric fields, e.g. electric discharge, plasma
• CPC Class Codes: C08F 220/10 Esters
• CPC Class Codes: C08F 283/04 on to polycarbonamides, polyesteramides or polyimides C08F283/004 takes precedence
• CPC Class Codes: C08F 299/06 from polyurethanes
• CPC Class Codes: C08G 18/48 Polyethers
• CPC Class Codes: C08G 18/671 Unsaturated compounds having only one group containing active hydrogen takes precedence on groups C08G18/675 - C08G18/69
• CPC Class Codes: C08G 18/795 formed by oligomerisation of mixtures of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates with aromatic isocyanates or isothiocyanates
• CPC Class Codes: C09D 151/00 Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds based on ABS polymers C09D155/02; Coating compositions based on derivatives of such polymers
• CPC Class Codes: G03F 7/032 with binders
• CPC Class Codes: G03F 7/037 the binders being polyamides or polyimides

Abstract

Release coatings are provided by including in a liquid monomer or prepolymer polymerizable by electromagnetic or ionizing radiation a waxy material of limited compatibility therein. Upon application of a film of such material by casting, coating or printing, a thin layer of the waxy material migrates to the surface to provide, after cure, the desired release properties. The thin surface layer of waxy material also tends to exclude oxygen from the film to permit radiant curing in air. Preferably the polymerizable liquid comprises acrylate monomers with or without unsaturated prepolymers co-polymerizable therewith dissolved therein. Novel prepolymers especially useful for providing release films and other radiation curable coatings are described, including the reaction product of polyamides, containing primary and secondary amine groups with unsaturated polybasic carboxylic acids and particular reaction products of polyether triols with toluene diisocyanate, modified with unsaturated monomers. Also described is the inclusion in the polymerizable liquid of a dispersed substantially linear polymer as shrink control and re-inforcing agent.

Claims

1. A method of producing a durable coating on the surface of a solid comprising the steps of:

modifying a polyamide containing primary and/or secondary amine groups, (internally and/or terminally) with unsaturated esters, anhydrides, and/or acids in ratios from 2;

1 to 10;

1 (unsaturated ester, acid or anhydride;

polyamide) thereby obtaining an unsaturated prepolymer which will copolymerize with acrylic and/or methacrylic monomers,

mixing with said prepolymer, as so modified, a quantity of acrylic and/or methacrylic monomer ester material, vinyl acetate, and/or vinyl pyrolidone, in proportion between about 1;

1 and 1;

20 (modified prepolymer to monomer ester);

coating said mixture on the surface of a sheet, plate or other solid body, and

irradiating said coating, as sensitized, with actinic radiation or, as unsensitized, with an electron beam, to produce a cured film.

2. A radiation curable pre-polymer method as defined in claim 1 in which:

said acrylate material is one selected from the group consisting of trimethylolpropane triacrylate, tetraethylene glycol diacrylate and acrylic acid, hydroxyethyl acrylate, neopentyl glycol diacrylate, acrylated epoxidized soybean oil, hexanediol diacrylate, 1,4-butanediol diacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, butyl acrylate, isodecylacrylate, octadecyl acrylate, corresponding methacrylates, and mixtures of two or more of them.

modifying a polyamide containing primary and/or secondary amine groups, (internally and/or terminally) with unsaturated esters, anhydrides, and/or acids in ratios from 2;

1 to 10;

1 (unsaturated ester, acid or anhydride;

polyamide) thereby obtaining an unsaturated prepolymer which will copolymerize with acrylic and/or methacrylic monomers,

mixing with said prepolymer, as so modified, a quantity of acrylic and/or methacrylic monomer ester material, vinyl acetate, and/or vinyl pyrolidone, in proportion between about 1;

1 and 1;

20 (modified prepolymer to monomer ester);

coating said mixture on the surface of a sheet, plate or other solid body, and

irradiating said coating, as sensitized, with actinic radiation or, as unsensitized, with an electron beam, to produce a cured film.

3. A method of producing a release coating for pressure sensitive adhesion or for transfer printing which is a method as defined in claim 1 in which method a small quantity of a hydrocarbon wax, oleamide, polysiloxane, silicone or silane, or of two or more of them is added to the mixture when said acrylic monomer ester material is mixed with said prepolymer.

4. A method of producing a durable coating as defined in claim 1 in which said prepolymer is a modified polyamide with primary and/or secondary amine groups, produced by heating a methyl or ethyl ester or mixed methyl and ethyl esters of one or more dicarboxy unsaturated acids, followed by evaporating off methanol, ethanol or both, and excess ethyl or methyl esters or both, completing such evaporation at low pressure in the presence of a small quantity of p-methoxyphenyl to inhibit premature polymerization.

5. A method of producing a durable coating as defined in claim 4 in which said ester of a dicarboxy unsaturated acid is a substance selected from the group consisting of dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl itaconate and mixtures thereof.

6. A method of producing a durable coating as defined in claim 1 in which said modified prepolymer is obtained by heating an unsaturated dicarboxylic acid or an anhydride of such an acid with a polyamide amine and in which after the reaction so produced a small quantity of p-methoxyphenol is added to prevent premature further polymerization.

7. A method of producing a durable coating as defined in claim 1 in which said modified prepolymer is obtained by heating 5-norbornene-2, 3 dicarboxyl anhydride with a polyamide amine, and then allowing the material to cool in the presence of a small quantity of p-methoxyphenol.

8. A method of producing a durable coating as defined in claim 1 in which said modified prepolymer is obtained by heating a polyamide polyamine with an ethyl or methyl ester, or both, of an unsaturated dicarboxylic acid, or 5-norbornene-2, 3 dicarboxylic acid, stripping off volatile material at a pressure of a fraction of a millimeter of mercury, followed by allowing the reaction product to cool in the presence of a small quantity of p-methoxyphenol.

9. A method of producing a durable coating as defined in claim 1 in which said modified prepolymer is a reaction product of a polyamide polyamine and a substance selected from the group consisting of ethyl and methyl esters of maleic, fumaric and itaconic acids and of 5-norbornene-2,3 dicarboxylic acid and anhydrides of such acids and mixtures thereof.

10. A method of producing a durable coating as defined in claim 1 in which said acrylic or methacrylic monomer ester material comprises one or more substances selected from the group consisting of trimethylolpropane triacrylate, hydroxyethyl methacrylate, neopentyl glycol diacrylate, acrylated epoxidized soybean oil, trimethylolpropane triacrylate, pentaerythritol, tri or tetraacrylate tetracthylene glycol diacrylate vinylacetate, vinylpynolidone, hydroxyethylacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, as well as the corresponding methacrylates, and an oxygen-barrier material such as stearyl acrylate.

11. A method of producing a durable coating as defined in claim 10 in which said acrylic monomer ester material comprises trimethylolpropane triacrylate and hydroxyethyl acrylate and includes an admixture of a sensitizer or initiator and a hydrocarbon, ester, or fluorocarbon wax, a waxy higher alkyl alcohol or acid, oleamide, polysiloxane or silane, or silicone, and in which the mixture is coated on a flexible sheet at a thickness in the range from about 0.1 to about 2.0 mils and thereafter exposed for at least 0.1 second to ultraviolet radiation of a medium pressure mercury lamp.

12. A method of producing a durable coating as defined in claim 10 in which said acrylic or methacrylic monomer ester material comprises trimethylolpropane triacrylate, acrylated epoxidized soybean oil, hexanediol diacrylate and stearyl acrylate and the resulting mixture is applied to a thickness in the range from about 0.1 to about 6 mils to a solid surface and thereafter exposed to 5 Mrad of electron beam irradiation in vacuum.

13. A method of producing a durable coating as defined in claim 10 in the form of ink applied to a surface by printing, in which said acrylic monomer ester material comprises trimethylol propane triacrylate, in which a pigment and a small quantity of stearyl acrylate is mixed in at the same time and in which thereafter a sensitizer or photoinitiator is mixed in, after which the resulting mixture is applied by printing as an ink with a film thickness between about 0.01 to about 0.4 mils to a surface to be printed, after which the printed surface is exposed for at least 0.1 second to ultraviolet radiation from a medium pressure mercury lamp.