Title: Method for preparing coatings using curable solid styrene-allyl alcohol copolymer based polyene and polythiol compositions

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Claims: What is claimed is:

1. A process which comprises:

A. applying to the surface of a substrate a solid layer of a curable composition consisting essentially of

1. a solid polyene containing at least 2 reactive unsaturated carbon to carbon bonds per molecule selected from the group consisting of polyene compounds having the general formula: ##EQU12## wherein Q is a styrene-allyl alcohol copolymeric moiety remaining after n hydroxyl groups of a styrene-allyl alcohol copolymer have reacted to form (i) n urethane linkages in Formula I and (ii) n ester linkages in Formula II; A and B are polyvalent organic radical members free of reactive carbon to carbon unsaturation and are independently selected from the group consisting of aryl, substituted aryl, aralkyl, substituted aralkyl, cycloalkyl, substituted cycloalkyl, alkyl and substituted alkyl containing 1 to 36 carbon atoms and mixtures thereof, said group members can be internally connected to one another by a chemically compatible linkage selected from the group consisting of --O--, --S--, carboxylate, carbonate, carbonyl, urethane and substituted urethane, urea and substituted urea, amide and substituted amide, amine and substituted amine and hydrocarbon; Z is a divalent chemically compatible linkage selected from the group consisting of -NH-C-O-,

--o-- and --S--; X is a member selected from the group consisting of:

a. --(CH.sub.2).sub.d --CR'=CHR

b. --O(CH.sub. 2).sub.d --CR'=CHR

c. --S-(CH.sub.2).sub.d -CR'=CHR

d. --(CH.sub.2).sub.d --C.tbd.CR

e. --O--(CH.sub.2).sub.d --C.tbd.CR

f. --S--(CH.sub.2).sub.d --C.tbd.CR

and mixtures thereof; where R and R' each are independently selected from the group consisting of hydrogen and methyl radicals; d, k, p and q are each integers from 0 to 1; y is an integer from 1 to 10; m and n are each integers of at least 1; with the proviso that when n is 1, y or m is at least 2; and

2.

2. a solid polythiol containing at least 2 thiol groups per molecule of the general formula: ##EQU13## wherein x is an integer of at least 2; E is a styrene-allyl alcohol copolymeric moiety remaining after removal of x hydroxyl groups from a styrene-allyl alcohol copolymer to form x ester linkages; and R.sub.3 is a polyvalent organic radical member free of reactive carbon to carbon unsaturation and is selected from the group consisting of aryl, substituted aryl, aralkyl, substituted aralkyl, cycloalkyl, substituted cycloalkyl, alkyl and substituted alkyl groups containing 1 to 16 carbon atoms and mixtures thereof, the total combined functionality of (1) the reactive unsaturated carbon to carbon bonds per molecular in the polyene and (2) the thiol groups per molecule in the polythiol being greater than 4;

B. exposing selected areas of said composition to a free radical generator, thereby curing the exposed areas of said composition; and

C. removing the unexposed uncured areas of the curable composition, thereby baring the surface of said substrate beneath the removed uncured areas of

the composition. 2. The process of claim 1 wherein

1. said solid polyene is selected from the group consisting of polyene compounds having the formula: ##SPC3##

wherein in Formula I, B is a polyvalent organic radical selected from the group consisting of ##EQU14## and mixtures thereof; X is a member selected from the group consisting of --CH.sub.2 --CH=CH.sub.2, --CH.sub.2 CH=CHCH.sub.3, --O--CH.sub.2 --CH=CH.sub.2 and --CH=CH.sub.2 and mixtures thereof, y is an integer of 1 or 2; and the integers q and n in Formula I and the Q radicals in Formulas I and II have the same meaning as in claim 1; and wherein in Formula II, n is an integer of at least 2 and X is a member selected from the group consisting of --CH=CH.sub.2, --CCH.sub.3 =CH.sub.2, --CH.sub.2 --CH=CH.sub.2 and mixtures thereof; and (2) the radical R.sub.3 in said solid polythiol selected from the group consisting of --CH.sub.2 --, ##EQU15## -CH.sub.2 CH.sub.2 -- and mixtures thereof; and said styrene-allyl alcohol copolymer reactants having an equivalent weight of about 300 .-+. 130 and a hydroxyl group content from about 4 to 10 percent by weight.

3. A composition of claim 2 wherein said solid polyene is a polyene having Formula I and q is an integer of 0, n is an integer of at least 2 and X member is --CH.sub.2 --CH=CH.sub.2 ; and the radical R.sub.3 in said solid polythiol is --CH.sub.2 --CH.sub.2 --; said styrene-allyl alcohol reactants having an equivalent weight of about 220 and a hydroxyl group content of about 7.7 percent by weight.

4. The process according to claim 1 wherein the composition is applied to the surface by a lamination process wherein a removable protective carrier film is used to apply said composition as an adherent preformed layer.

5. The process according to claim 1 wherein the composition is applied to the surface as a coating in solution and the solvent is removed.

6. The process according to claim 1 wherein the free radical generator is actinic radiation.

7. The process according to claim 6 wherein the actinic radiation is actinic laser radiation.

8. The process according to claim 6 wherein the actinic radiation is ultraviolet light having a wavelength between about 2000A and about 4000A.

9. The process according to claim 1 wherein at least the surface of said substrate is metallic.

10. The process according to claim 9 further including the steps of: (D) etching the exposed metallic areas of said substrate to the desired depth, and (E) optionally removing the cured areas of said composition.

11. The process according to claim 10 wherein the surface is a metal cladding on an insulating substrate.

12. The process of claim 6 wherein said composition contains from 0.005 to 50 parts by weight of 100 parts by weight of said polyene and said polythiol of a photocuring rate accelerator.

13. The process according to claim 1 further including the steps of (D) depositing a layer of metal onto the bared areas of said surface, and thereafter (E) optionally removing the cured composition from said substrate.

14. The process according to claim 13 wherein the substrate is an insulating substrate.

15. The process according to claim 13 wherein the deposition of said metal is electroless.

16. The process according to claim 13 wherein the surface of said substrate is a metal cladding.

17. The process according to claim 16 wherein in step (E) the cured portion of said composition is removed from said surface, and thereafter the unprotected unplated areas of said metal cladding are etched.

18. The process according to claim 13 wherein said metal is deposited by soldering onto a metallic surface.

19. The process according to claim 1 wherein said substrate is perforated.

20. The process according to claim 1 wherein the substrate is a plastic.

Other info:

Inventors: Morgan, Charles R. (Silver Spring, MD, US)

Application Number: 425748
Filing Date: 1973-12-18
Publication_date: 1976-02-03
Assignee: W. R. Grace & Co. (New York, NY)
Primary Class(es): 430/284.1 156/230, 427/273, 427/517, 427/520, 428/901, 430/275.1, 430/285.1, 430/287.1, 430/296, 430/315, 430/318, 430/323, 430/324, 430/413, 430/945, 522/2, 522/
Other Classes:
US Patent Ref:

2630430	Mar, 1953	Shokal et al.	260/23.
3340236	Sep, 1967	Greenlee et al.	260/78.
3615450	Oct, 1971	Werber et al.	96/35.
3619393	Nov, 1971	Stahly	204/159.
3645730	Feb, 1972	Frank et al.	96/28.
3719638	Mar, 1973	Huemmer et al.	260/77.

Other Refs:
Primary Examiner: Newsome, John H.
Assistant Examiner:
Attorney: McCandless; Giedre M.