Radiation-curable thermoplastic coating

• US 4,654,233 A
• Filed: 11/21/1984
• Issued: 03/31/1987
• Est. Priority Date: 11/21/1984
• Status: Expired due to Fees

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Landin, Heather V., Grant, Richard J., Johnson, Gilbert C.
• Primary Examiner(s): Jacobs, Lewis T.
• Assistant Examiner(s): Short, Patricia A.
• Application Number:
  US06/673,873
• Time in Patent Office: 860 Days
• Field of Search: 525/54.22, 525/54.3, 525/54.21, 525/112, 525/111, 526/238.21, 523/448, 428/481, 427/379
• US Class Current: 427/379
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C09D 167/06 Unsaturated polyesters having carbon-to-carbon unsaturation
• CPC Class Codes: Y10T 428/3179 Next to cellulosic

Abstract

A coating composition is provided. The coating composition is a curable blend of ethylenically unsaturated polyester and ethylenically unsaturated thermoplastic polymers. The composition is capable of providing a thermoplastic, soluble, sandable, intermediate-stage coating and, when cured, a final stage coating which is unaffected by acetone placed on the final stage coating for two hours at 22° C., has a percent haze value of 15% or less, and is unaffected when subjected to a Wet Print Test.

Claims

1. A coating composition comprising a curable blend of

(a) 20 to 80 weight percent of an ethylenically unsaturated polyester comprising the condensation or addition product of a polyhydroxy polyester comprising the reaction product of at least one organic diepoxide, and at least one saturated or unsaturated dicarboxylic acid, and an effective amount of polymerizable ethylenically unsaturated compound having sufficient reactive functional groups with the hydroxyl groups of said polyhydroxy polyester oligomer to provide to the ethylenically unsaturated polyester an ethylenic unsaturation equivalent weight of less than about 500, and

(b) 20 to 80 weight percent of ethylenically unsaturated thermoplastic polymers selected from ethylenically unsaturated cellulose esters, ethylenically unsaturated polyvinyl acetate copolymers, ethylenically unsaturated acrylic copolymers, or ethylenically unsaturated azlactone copolymers,

said composition capable of providing a thermoplastic, soluble, sandable, intermediate-stage coating and a final stage coating which is unaffected by acetone placed on the final stage coating for 30 minutes at 22°

C., which final stage coating has a percent haze value of 15% or less, and which final stage coating is unaffected when subjected to a Wet Print Test.

2. The coating composition of claim 1 wherein said ethylenically unsaturated polyester further comprises monocarboxylic acid monoepoxide, or combinations thereof.

3. The coating composition of claim 1 wherein said ethylenically unsaturated polyester is represented by the formula:

##STR21## wherein each R¹ and R² are independently a divalent organic group having 2 to 40 carbon atoms selected from saturated or unsaturated straight or branched aliphatic or cycloaliphatic groups or aromatic groups;

each R³ is independently hydrogen, or an alkylene group having 2 or 3 carbon atoms that together with atoms in R¹ and the --CH--CH-- group form a 5- or 6-membered trivalent cycloalkane group,

each R⁴ is independently ##STR22## --H or --CH₃ ;

wherein R⁷ is a monovalent organic radical having 1 to 24 carbon atoms and is selected from saturated or unsaturated straight or branched aliphatic groups or aromatic groups;

R⁸ is an alkylene group having 2 to 12 carbon atoms;

R⁹ is a divalent organic group selected from linear, branched or cyclic alkylene groups having 2 to 40 carbon atoms, phenylene groups, naphthylene groups or phenylenemethylenephenylene groups and R¹⁰ is hydrogen or an alkyl group having 1 to 4 carbon atoms;

R⁵ is selected from ##STR23## where R² and R⁷ are as defined above and R¹¹ is selected from hydrogen, ##STR24## where R¹, R³, and R⁴ are as defined above and R¹² is a monovalent organic radical having 1 to 20 carbon atoms and is selected from saturated or unsaturated straight or branched chain aliphatic groups or aromatic groups;

R⁶ is selected from R¹¹ or ##STR25## where R¹, R³, R⁴, R⁷ and R¹¹ are as defined above;

and n is a number having an average value of about 1 to 10, except where R⁵ is ##STR26## n is a number having an average value of about 0 to 10.

4. An ethylenically unsaturated polyester according to claim 3 wherein said divalent organic group R⁹ is substituted by up to four lower alkyl groups having 1 to 4 carbon atoms.

5. An ethylenically unsaturated polyester according to claim 3 represented by the formula ##STR27##

6. An ethylenically unsaturated polyester according to claim 5 wherein each of R², R⁴ and R⁷ contain a polymerizable ethylenically unsaturated group.

7. The coating composition of claim 1 wherein said ethylenically unsaturated thermoplastic cellulose ester comprises the condensation or addition product of (a) a cellulose ester of cellulose and saturated aliphatic monocarboxylic acids having 2 and 4 carbon atoms or aromatic monocarboxylic acids, said cellulose ester having an average of 0.1 to 2.0 unreacted hydroxyl groups per anhydroglucose unit and (b) a chemically effective amount of polymerizable ethylenically unsaturated compound having sufficient reactive functionality with the hydroxyl groups of said cellulose ester, to yield an ethylenically unsaturated cellulose ester wherein up to 100% of the unreacted hydroxyl groups have been converted to polymerizable unsaturated groups.

8. The polymerizable ethylenically unsaturated cellulose esters according to claim 7 represented by the following formula:

space="preserve" listing-type="equation">[C.sub.6 H.sub.7 O.sub.2 (OR.sup.13).sub.x (OR.sup.14).sub.3-x ].sub.m

wherein each R¹³ is independently selected from H, ##STR28## where R, R⁸, R⁹ and R¹⁰ are as defined above;

R¹⁴ is selected from ##STR29## where R⁷ is as defined above, x is 0.1 to 2.0;

m is a number of at least about 20 or larger, and the various OR¹³ and OR¹⁴ groups are randomly distributed in the m subunits, and have an unsaturated equivalent weight of less than about 1000.

9. A polymerizable ethylenically unsaturated cellulose ester according to claim 8 having the formula ##STR30## where R¹⁵ is independently selected from --C₂ H₅ or --C₃ H₇, the sum of a and b is 3-x, each of a and b are 0 to 2.9 and the a, b and x groups are randomly distributed in the m subunits of the cellulose ester.

10. A wood substrate having a protective coating thereon comprising a cured coating of the composition of claim 1.

11. A method for protectively coating a substrate comprising the steps of

(a) coating said substrate with the composition of claim 1, and

(b) drying said coating,

(c) curing said coating.

12. The method of claim 11, wherein said coating is sanded after said drying step, prior to said curing step.

13. A coating composition comprising a blend of (a) 20 to 80 weight percent of ethylenically unsaturated polyester which is the condensation or addition product of a polyhydroxy polyester comprising the reaction product of at least one organic diepoxide, and at least one saturated or unsaturated dicarboxylic acid, and an effective amount of polymerizable ethylenically unsaturated compound having sufficient reactive functional groups with the hydroxyl groups of said polyhydroxy polyester oligomer to provide to the ethylenically unsaturated polyester an ethylenic unsaturation equivalent weight of less than about 500, and (b) 20 to 80 weight percent of an ethylenically unsaturated thermoplastic cellulose ester which is the condensation or addition product of a cellulose ester of cellulose and saturated aliphatic monocarboxylic acids having 2 to 4 carbon atoms or aromatic monocarboxylic acids, said cellulose ester having an average of 0.1 to 2.0 unreacted hydroxyl groups per anhydroglucose unit and a chemically effective amount of polymerizable ethylenically unsaturated compound having sufficient reactive functionality with the hydroxyl groups of said cellulose ester, to yield an ethylenically unsaturated cellulose ester wherein up to 100% of the unreacted hydroxyl groups have been converted to polymerizable unsaturated groups.

14. A coating composition comprising a blend of (a) 20 to 80 weight percent of an ethylenically unsaturated polyester which is the addition product of (i) a polyhydroxyl polyester comprising the reaction product of the diglycidyl ether of Bisphenol A, itaconic acid, and acrylic acid, the molar ratio being 1.0/0.5/1.0, respectively, and (ii) isocyanatoethyl methacrylate and (b) 20 to 80 weight percent of an ethylenically unsaturated thermoplastic polymer which is the addition product of cellulose acetate propionate and isocyanatoethyl methacrylate.

15. A coating composition comprising a curable blend of

(a) 20 to 80 weight percent of an ethylenically unsaturated polyester comprising the condensation or addition product of a polyhydroxy polyester comprising the reaction product of at least one organic diepoxide, and at least one saturated or unsaturated dicarboxylic acid, and an effective amount of polymerizable ethylenically unsaturated compound having sufficient reactive functional groups with the hydroxyl groups of said polyhydroxy polyester oligomer to provide to the ethylenically unsaturated polyester an ethylenic unsaturation equivalent weight of less than about 500, and

(b) 20 to 80 weight percent of an ethylenically unsaturated cellulose ester comprising the reaction product of a cellulose ester of cellulose and saturated aliphatic monocarboxylic acids having 2 to 4 carbon atoms or aromatic monocarboxylic acids, said cellulose ester having an average of about 0.1 to 2.0 unreacted hydroxyl groups per anhydroglucose unit, and a polymerizable ethylenically unsaturated compound having an isocyanato group reactive with the hydroxyl groups of the cellulose ester, said composition capable of providing a thermoplastic, soluble, sandable, intermediate-stage coating and a final stage coating which is unaffected by acetone placed on the final stage coating for 30 minutes at 22°

C., which final stage coating has a percent haze value of 15% or less, and which final stage coating is unaffected when subjected to a Wet Print Test.