METHOD AND FORMULATIONS FOR THE MANUFACTURE OF COATED ARTICLES AND COMPOSITES

• US 20150118456A1
• Filed: 11/05/2014
• Published: 04/30/2015
• Est. Priority Date: 05/07/2012
• Status: Active Grant

• Current Assignee: Mercene Labs AB
• Original Assignee: Mercene Labs AB
• Inventors: CARLBORG, Carl Fredrik, HARALDSSON, Tommy
• Granted Patent: US 9,523,019 B2
• Time in Patent Office: Days
• US Class Current: 428/201
• CPC Class Codes: B05D 1/02 performed by spraying
• CPC Class Codes: B05D 1/28 performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
• CPC Class Codes: B05D 1/305 Curtain coating
• CPC Class Codes: B05D 3/06 by exposure to radiation B05D3/02 takes precedence ; plasma treatment B05D3/141
• CPC Class Codes: B05D 3/067 Curing or cross-linking the coating
• CPC Class Codes: B05D 7/50 Multilayers
• CPC Class Codes: B05D 7/58 No clear coat specified
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 283/105 on to unsaturated polymers containing more than one epoxy radical per molecule
• CPC Class Codes: C08G 59/4064 sulfur containing compounds C08G59/4021, C08G59/4028 take precedence
• CPC Class Codes: C09D 163/00 Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• CPC Class Codes: C09D 163/04 Epoxynovolacs
• 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: G03F 7/0275 with dithiol or polysulfide compounds
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: H05K 3/0091 Apparatus for coating printed circuits using liquid non-metallic coating compositions
• CPC Class Codes: Y10T 428/24851 Intermediate layer is discontinuous or differential
• CPC Class Codes: Y10T 428/269 including synthetic resin or polymer layer or component
• CPC Class Codes: Y10T 428/31515 As intermediate layer
• CPC Class Codes: Y10T 428/31522 Next to metal

Abstract

An object with a coating comprising: a) covalent bonds formed by reaction of a thiol group and a carbon-carbon double bond, b) covalent bonds formed by reaction of a thiol group and epoxide group, c) covalent bonds formed by a reaction of a carbon-carbon double bond and an epoxide group, said coating comprising a first primer coating and a second coating, said coating comprising covalent bonds between said first and second coatings, said first primer coating comprising covalent cross links between compounds, in the first coating the fraction (r3=ta/tc) of unreacted thiol groups (ta) to thiol groups which have reacted to form a covalent bond (tc) does not exceed 0.11, wherein the half height peak width of tan delta does not exceed 30° C. Advantages of the dual cure composition is that excellent strength is obtained and that the second curing is slow compared to the first initial curing.

Claims

1. A method for at least partially coating an object, said method comprising the steps:

a) applying at least partially to said object at least one of—

;

i. a compound comprising at least two thiol groups,

ii. a compound comprising at least two carbon-carbon double bonds, and

iii. a compound comprising at least two epoxide groups, and

wherein ratio (r₁=t/cc) of the total number of thiol groups (t) in all of the above compounds and the total number of carbon-carbon double bonds (cc) in all of the above compounds is selected from the group consisting of 0.1≦

r₁≦

0.9 and 1.1≦

r₁≦

20,

with the proviso that if the ratio r₁ is in the interval;

0.1≦

r₁≦

0.9, then at least one homopolymerizing ene-compound is used,

wherein ratio (r₂=t/e) of the total number of thiol groups (t) in all of the above compounds and the total number of epoxide groups (e) in all of the above compounds is in the range 0.3≦

r₂≦

20,

b) initiating a reaction of at least a part of the applied compound comprising at least two thiol groups with at least one of

i. at least a part of the applied compound comprising at least two carbon-carbon double bonds and,

ii. at least a part of the applied compound comprising at least two epoxide groups,

iii. at least a part of the applied compound comprising at least one carbon-carbon double bond and at least one epoxide group,

to obtain an intermediate at least partial coating, wherein said coating comprises at least one compound comprising an unreacted group selected from the group consisting of an unreacted thiol group, and an unreacted epoxide group,

c) initiating a reaction of at least a part of said at least one compound comprising an unreacted group,

wherein at least one further coating is applied after step b) and before step c), to obtain to a final coated article.

2. The method according to claim 1, wherein the reaction between at least a part of the applied compound comprising at least two thiol groups and at least a part of the applied compound comprising at least one or two carbon-carbon double bonds is initiated with at least one selected from the group consisting of actinic radiation, and elevated temperature.

3. The method according to claim 1, wherein the reaction of the at least one compound comprising an unreacted group selected from the group consisting of an unreacted thiol group and an unreacted epoxide group is initiated with at least one selected from the group consisting of actinic radiation, and elevated temperature.

4. The method according to claim 1, wherein the reaction of the at least one compound comprising an unreacted group selected from the group consisting of an unreacted thiol group and an unreacted epoxide group is mediated with a basic compound.

5. The method according to claim 1, wherein step b) and c) are initiated simultaneously.

6. The method according to claim 1, wherein said at least one further coating comprises at least one compound selected from the group consisting of a compound reactive with a thiol forming a covalent bond and a compound reactive with an epoxide to form a covalent bond.

7. The method according to claim 1, wherein said at least one further coating comprises at least one compound comprising at least one chemical group selected from the group consisting of a hydroxyl group, an amine group, a thiol group, an anhydride group, a cyanoacrylate group, an epoxide group, and a metal oxide.

8. The method according to claim 1, wherein said at least one further coating comprises at least one compound comprising a chemical group selected from the group consisting of an acrylate, a methacrylate, a thiol, an isocyanate, a maleate, a fumarate, a vinyl ether, an alkene, an alkyne, an allyl ether.

9. The method according to claim 1, wherein said at least one further coating comprises at least one selected from the group consisting of a metal, a polymer sheet, and a powder.

10. The method according to claim 1, wherein the surface of said object to be at least partially coated comprises at least one selected from the group consisting of a metal, a rubber, silicon, a thermoplastic elastomer, cellulose fibers, a textile, wood, a composite material, concrete, and stone.

11. The method according to claim 1, wherein the object to be at least partially coated is a printed circuit board.

12. The method according to claim 1, wherein said compound comprising at least two thiol groups is selected from the group consisting of pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetramercaptopropionate (PETMP);

1-octanethiol;

butyl 3-mercaptopropionate;

2,4,6-trioxo-1,3,5-triazina-triy (triethyl-tris (3-mercapto propionate);

1,6-Hexanedithiol;

2,5-dimercaptomethyl-1,4-dithiane, pentaerythritol tetramercaptoacetate, trimethylolpropane trimercaptoacetate, 2,3-dimercapto-1-propanol, 2,3-(dimercaptoethylthio)-1-mercaptopropane, 1,2,3-trimercaptopropane, toluenedithiol, xylylenedithiol, 1,8-octanedithiol, and trimethylolpropane tris(3-mercaptopropionate), and glycol dimercaptopropionate and pentaerythritol tetramercaptopropionate (PETMP).

13. The method according to claim 1, wherein said compound comprising at least two carbon-carbon double bonds is selected from the group consisting of triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione;

triethyleneglycol divinyl ether (TEGDVE);

trimethylolpropane diallyl ether;

1,6-heptadiyne;

1,7-octadiyne;

bis-2,2-[4-(2-[norborn-2-ene-5-carboxylate]ethoxy)phenyl]propane (BPAEDN);

1,6-hexanediol di-(endo,exo-norborn-2-ene-5-carboxylate) (HDDN);

trimethylolpropane tri-(norborn-2-ene-5-carboxylate) (TMPTN);

pentaerythritoltri-(norborn-2-ene-5-carboxylate) (PTN3);

pentaerythritol tetra-(norborn-2-ene-5-carboxylate) (PTN4);

tricyclodecane dimethanol di-(endo, exo-norborn-2-ene-5-carboxylate) (TCDMDN); and

di(trimethylolpropane) tetra-(norbom-2-ene-5-carboxylate) (DTMPTN).

14. The method according to claim 1, wherein said compound comprising at least two epoxide groups is selected from the group consisting of Tris(2,3-epoxidepropyl) isocyanurate, trimethylolpropane triglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, poly(ethylene glycol) diglycidyl ether, bisphenol A diglycidyl ether 1,2,5,6-diepoxidecyclooctane, 1,2,7,8-diepoxideoctane, 1,2-Epoxide-5-hexene, 1,4-cyclohexanedimethanol diglycidyl ether, 3,4-epoxidecyclohexylmethyl 3,4-epoxidecyclohexanecarboxylate, 4,4′

-methylenebis(N,N-diglycidylaniline), bis[4-(glycidyloxy)phenyl]methane, bis[4-(glycidyloxy)phenyl]methane, diglycidyl 1,2-cyclohexanedicarboxylate, N,N-diglycidyl-4-glycidyloxyaniline, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, and tris(4-hydroxyphenyl)methane triglycidyl ether.

15. The method according to claim 1, wherein said compound comprising at least two epoxide groups is allylglycidylether.

16. The method according to claim 1, wherein the thickness of the compounds added in step a) is in the interval 2-100 μ

m.

17. The method according to claim 1, wherein said at least one homopolymerizing ene-compound is selected from the group consisting of acrylate and methacrylate.

18. A coated object comprising a coating which is at least partially applied to said object, said coating comprising:

a) covalent bonds formed by reaction of a thiol group and a carbon-carbon double bond,

b) covalent bonds formed by reaction of a thiol group and epoxide group,

c) covalent bonds formed by a reaction of a carbon-carbon double bond and an epoxide group,

said coating comprising a first coating and a second coating,

said coating comprising covalent bonds between said first and second coatings,

said first coating comprising covalent cross links between compounds,

in the first coating the fraction (r₃=ta/tc) of unreacted thiol groups (ta) to thiol groups which have reacted to form a covalent bond (tc) does not exceed 0.11,

wherein, for the first coating the half height peak width of tan delta does not exceed 30°

C., said tan delta peak temperature (Tp) and said half height peak width being obtained from a viscoelasticity (tan delta) temperature distribution curve which is determined using a viscoelastic spectrometer at a frequency of 1 Hz, an initial strain of 1%, an amplitude of 15 μ

m and a temperature elevating rate of 5°

C./min, temperatures being equal to and greater than Tp to the temperature defined by the point of intersection of the line of tan delta=1/2P, wherein P is the peak value of tan δ

, with the distribution curve.

19. The coated object according to claim 18, wherein said second coating comprises at least one compound comprising at least one chemical group selected from the group consisting of a hydroxyl group, an amine group, a thiol group, an anhydride group, a cyanoacrylate group, an epoxide group, and a metal oxide.

20. The coated object according to claim 18, wherein said second coating comprises at least one compound comprising a chemical group selected from the group consisting of an acrylate, a methacrylate, a thiol, an isocyanate, a maleate, a fumarate, a vinyl ether, an alkene, an alkyne, an allyl ether.

21. The coated object according to claim 18, wherein said second coating comprises at least one selected from the group consisting of a metal, a polymer sheet, and a powder.

22. The coated object according to claim 18, wherein the surface of said object comprises at least one selected from the group consisting of a metal, a rubber, silicon, a thermoplastic elastomer, cellulose fibers, a textile, wood, a composite material, concrete, and stone.

23. The coated object according to claim 18, wherein the object to be at least partially coated is a printed circuit board.

24. The coated object according to claim 18, wherein the first coating comprises at least one compound selected from the group consisting of pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetramercaptopropionate (PETMP);

1-octanethiol;

butyl 3-mercaptopropionate;

2,4,6-trioxo-1,3,5-triazina-triy (triethyl-tris (3-mercapto propionate);

1,6-Hexanedithiol;

2,5-dimercaptomethyl-1,4-dithiane, pentaerythritol tetramercaptoacetate, trimethylolpropane trimercaptoacetate, 2,3-dimercapto-1-propanol, 2,3-(dimercaptoethylthio)-1-mercaptopropane, 1,2,3-trimercaptopropane, toluenedithiol, xylylenedithiol, 1,8-octanedithiol, and trimethylolpropane tris(3-mercaptopropionate), and glycol dimercaptopropionate and pentaerythritol tetramercaptopropionate (PETMP), wherein at least one thiol group has formed a covalent bond with at least one selected from a carbon-carbon double bond and an epoxide group.

25. The coated object according to claim 18, wherein the first coating comprises at least one compound selected from the group consisting of triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione;

triethyleneglycol divinyl ether (TEGDVE);

trimethylolpropane diallyl ether;

1,6-heptadiyne;

1,7-octadiyne;

bis-2,2-[4-(2-[norborn-2-ene-5-carboxylate]ethoxy)phenyl]propane (BPAEDN);

1,6-hexanediol di-(endo,exo-norborn-2-ene-5-carboxylate) (HDDN);

trimethylolpropane tri-(norborn-2-ene-5-carboxylate) (TMPTN);

pentaerythritoltri-(norborn-2-ene-5-carboxylate) (PTN3);

pentaerythritol tetra-(norborn-2-ene-5-carboxylate) (PTN4);

tricyclodecane dimethanol di-(endo, exo-norborn-2-ene-5-carboxylate) (TCDMDN); and

di(trimethylolpropane) tetra-(norbom-2-ene-5-carboxylate) (DTMPTN), wherein at least one carbon-carbon double bond has formed a covalent bond with at least one selected from a thiol group and an epoxide group.

26. The coated object according to claim 18, wherein the first coating comprises at least one compound selected from the group consisting of Tris(2,3-epoxidepropyl) isocyanurate, trimethylolpropane triglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, poly(ethylene glycol) diglycidyl ether, bisphenol A diglycidyl ether 1,2,5,6-diepoxidecyclooctane, 1,2,7,8-diepoxideoctane, 1,2-Epoxide-5-hexene, 1,4-cyclohexanedimethanol diglycidyl ether, 3,4-epoxidecyclohexylmethyl 3,4-epoxidecyclohexanecarboxylate, 4,4′

-methylenebis(N,N-diglycidylaniline), bis[4-(glycidyloxy)phenyl]methane, bis[4-(glycidyloxy)phenyl]methane, diglycidyl 1,2-cyclohexanedicarboxylate, N,N-diglycidyl-4-glycidyloxyaniline, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, and tris(4-hydroxyphenyl)methane triglycidyl ether, wherein at least one epoxide group has formed a covalent bond with at least one selected from a thiol group and a carbon-carbon double bond.

27. The coated object according to claim 18, wherein the thickness of the coating is in the interval 0.01-2000 μ

m.

28. The coated object according to claim 18, wherein the coating forms a barrier impermeable to liquid.