Coating composition and process for preparing synthetic resin shaped articles by using same

• US 4,388,345 A
• Filed: 01/27/1982
• Issued: 06/14/1983
• Est. Priority Date: 02/04/1981
• Status: Expired due to Fees

• Current Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Original Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Inventors: Sasaki, Isao, Kushi, Kenji, Kishida, Kazuo, Tamura, Misao
• Primary Examiner(s): Newsome, John H.
• Application Number:
  US06/343,221
• Time in Patent Office: 503 Days
• Field of Search: 427/54.1, 427/44, 427/162, 427/164, 428/412, 204/159.22
• US Class Current: 427/512
• CPC Class Codes: C08F 222/105 of pentaalcohols
• CPC Class Codes: C08J 2331/00 Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
• CPC Class Codes: C08J 7/16 with polymerisable compounds
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: Y10T 428/31507 Of polycarbonate

Abstract

A shaped article of synthetic resins, such as polydiethylene glycol bisallylcarbonate, is coated with the following coating composition and then irradiated with ultraviolet rays, whereby the coating composition deposited on the shaped article is cured to form a coating film having an excellent abrasion resistance, surface smoothness, adhesion to the substrate resin, flexibility, heat resistance, solvent resistance and durability. The coating composition comprised of (a) a mixture of, based on the weight of the mixture, (i) 25-99.95 wt. % of at least one polyfunctional monomer having at least three acryloyloxy or methacryloyloxy groups, (ii) 0-50 wt. % of at least one mono- or bi-functional monomer having one or two polymerizable unsaturated groups and (iii) 0.05-25 wt. % of at least one organic acid which has at least one halogen substituent (fluorine, chlorine or bromine) and which is liquid at normal temperature and pressure, and (b) 0.01-10 wt. parts, based on 100 wt. parts of said mixture, of a photosensitizer. The coating composition may contain 0.05-25 wt. % of at least one compound having an acrylamide or methacrylamide group and a hydroxyl group or groups.

Claims

1. A coating composition which comprises:

(a) a mixture comprised of, based on the weight of said mixture, (i) 25 to 99.95% by weight of at least one polyfunctional monomer having at least three acryloyloxy or methacryloyloxy groups in the molecule, (ii) 0 to 50% by weight of at least one mono- or bi-functional monomer having one or two polymerizable unsaturated groups in the molecule and (iii) 0.05 to 25% by weight of at least one organic acid which has at least one halogen substituent selected from the group consisting of fluorine, chlorine or bromine and which is liquid at normal temperature and pressure, and

(b) 0.01 to 10 parts by weight, based on 100 parts by weight of said mixture, of a photosensitizer.

3. A coating composition according to claim 1 wherein the average molecular weight per polymerizable unsaturated group present in the total amount of (i) the polyfunctional monomer containing at least three acryloyloxy or methacryloyloxy groups and (ii) the polymerizable unsaturated group-containing mono- or bi-functional monomer is not higher than about 300.

5. A coating composition according to claim 1 or 2 wherein the acryloyloxy and methacryloyloxy groups in the polyfunctional monomer containing at least three acryloyloxy or methacryloyloxy groups are bonded to each other through at least one linkage selected from the group consisting of a hydrocarbon linkage, an ether linkage or an ester linkage, said linkage having 1 to 30 carbon atoms and 0 to 10 oxygen atoms.

6. A coating composition according to claim 1 or 2 wherein the mono- or bi-functional monomer has an acryloyloxy or methacryloyloxy group or groups as the polymerizable unsaturated group or groups.

8. A coating composition according to claim 1 or 2 wherein the halogen substituent-having organic acid is selected from the group consisting of monochloroacetic acid, dichloroacetic acid and trichloroacetic acid.

2. A coating composition which comprises:

(a) a mixture comprised of, based on the weight of said mixture, (i) 25 to 99.90% by weight of at least one polyfunctional monomer having at least three acryloyloxy or methacryloyloxy groups in the molecule, (ii) 0 to 49.95% by weight of at least one mono- or bi-functional monomer having one or two polymerizable unsaturated groups in the molecule, (iii) 0.05 to 25% by weight of at least one compound having an acrylamide or methacrylamide group and a hydroxyl group in the molecule and (iv) 0.05 to 25% by weight of at least one organic acid which has at least one halogen substituent selected from the group consisting of fluorine, chlorine or bromine and which is liquid at a normal temperature and pressure, and

(b) 0.01 to 10 parts by weight, based on 100 parts by weight of said mixture, of a photosensitizer.

4. A coating composition according to claim 2 wherein the average molecular weight per polymerizable unsaturated group present in the total amount of (i) the polyfunctional monomer containing at least three acryloyloxy or methacryloyloxy groups, (ii) the polymerizable unsaturated group-containing mono- or bi-functional monomer and (iii) said compound having an acrylamide or methacrylamide group and a hydroxyl group or groups is not higher than about 300.

7. A coating composition according to claim 2 wherein said compound having an acrylamide or methacrylamide group and a hydroxyl group or groups in the molecule is selected from the group consisting of N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, N-hydroxylpropyl acrylamide and hydroxymethyl diacetone acrylamide.

9. A process for the preparation of a synthetic resin shaped article made of polydiethylene glycol bisallylcarbonate, which comprises coating the surface of a synthetic resin shaped article made of polydiethylene glycol bisallylcarbonate with a coating composition and irradiating the coated shaped article with ultraviolet rays to form on the surface of the synthetic resin shaped article a crosslinked and cured film exhibiting good abrasion resistance and adhesion, wherein said coating composition comprises:

(a) a mixture comprised of, based on the weight of said mixture, (i) 25 to 99.95% by weight of at least one polyfunctional monomer having at least three acryloyloxy or methacryloyloxy groups in the molecule, (ii) 0 to 50% by weight of at least one mono- or bi-functional monomer having one or two polymerizable unsaturated groups in the molecule and (iii) 0.05 to 25% by weight of at least one organic acid which has at least one halogen substituent selected from the group consisting of fluorine, chlorine or bromine and which is liquid at a normal temperature and pressure, and

(b) 0.01 to 10 parts by weight, based on 100 parts by weight of said mixture, of a photosensitizer.

11. A process according to claim 9 wherein the average molecular weight per polymerizable unsaturated group present in the total amount of (i) the polyfunctional monomer containing at least three acryloyloxy or methacryloyloxy groups and (ii) the polymerizable unsaturated group-containing mono- or bi-functional monomer is not higher than about 300.

10. A process for the preparation of a synthetic resin shaped article made of polydiethylene glycol bisallylcarbonate, which comprises coating the surface of a synthetic resin shaped article made of polydiethylene glycol bisallylcarbonate with a coating composition and irradiating the coated shaped article with ultraviolet rays to form, on the surface of the synthetic resin shaped article, a crosslinked and cured film exhibiting good abrasion resistance and adhesion, wherein said coating composition comprises:

(a) a mixture comprised of, based on the weight of said mixture, (i) 25 to 99.90% by weight of at least one polyfunctional monomer having at least three acryloyloxy or methacryloyloxy groups in the molecule, (ii) 0 to 49.95% by weight of at least one mono- or bi-functional monomer having one or two polymerizable unsaturated groups in the molecule, (iii) 0.05 to 25% by weight of at least one compound having an acrylamide or methacrylamide group and a hydroxyl group or groups in the molecule and (iv) 0.05 to 25% by weight of at least one organic acid which has at least one halogen substituent selected from the group consisting of fluorine, chlorine or bromine and which is liquid at a normal temperature and pressure, and

(b) 0.01 to 10 parts by weight, based on 100 parts by weight of said mixture, of a photosensitizer.

12. A process according to claim 10 wherein the average molecular weight per polymerizable unsaturated group present in the total amount of (i) the polyfunctional monomer containing at least three acryloyloxy or methacryloyloxy groups, (ii) the polymerizable unsaturated group-containing mono- or bi-funtional monomer and (iii) said compound having an acrylamide or methacrylamide group and a hydroxyl group or groups is not higher than about 300.

13. A process according to claim 9 or 10 wherein the acryloyloxy and methacryloyloxy groups in the polyfunctional monomer containing at least three acryloyloxy or methacryloyloxy groups are bonded to each other through at least one linkage selected from the group consisting of a hydrocarbon linkage, an ether linkage and an ester linkage, said linkage having 1 to 30 carbon atoms and 0 to 10 oxygen atoms.

14. A process according to claim 9 or 10 wherein the mono- or bi-functional monomer has an acryloyloxy or methacryloyloxy group or groups as the polymerizable unsaturated group or groups.

15. A process according to claim 10 wherein said compound, having an acrylamide or methacrylamide group and a hydroxyl group or groups in the molecule, is selected from the group consisting of N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, N-hydroxylpropyl acrylamide and hydroxymethyl diacetone acrylamide.

16. A process according to claim 9 or 10 wherein the halogen substituent-having organic acid is selected from the group consisting of monochloroacetic acid, dichloroacetic acid and trichloroacetic acid.

17. A process according to claim 9 or 10 wherein the polydiethylene glycol bisallylcarbonate shaped article is treated with an alkali prior to said coating.

18. A process according to claim 17 wherein said alkali treatment is carried out by using an aqueous sodium hydroxide or potassium hydroxide solution having a concentration of from 1 to 30% by weight at a temperature of from 50°

to 90°

C.

19. A process according to claim 18 wherein said alkali treatment is carried out by dipping the polydiethylene glycol bisallylcarbonate shaped article in said aqueous sodium hydroxide or potassium hydroxide solution for a period of from 5 to 120 seconds wherein said shaped article is introduced into and withdrawn from said aqueous alkali solution at a rate of at least 3 cm/sec.

20. A process according to claim 18 or 19 wherein the polydiethylene glycol bisallylcarbonate shaped article coated with the aqueous sodium hydroxide or potassium hydroxide solution is washed with water before said aqueous alkali solution deposited on the surface of said shaped article dries.

21. A process according to claim 20 wherein said washing with water is carried out within 30 seconds from the withdrawal of said shaped article from said aqueous alkali solution.