Process for the preparation of radiation-curable, water-thinnable vinyl ester resins

Claim 2

A process for preparing sulfonium-stabilized, water-compatible, radiation-curable vinyl ester compounds wherein epoxy compounds having on the average at least one pendant or terminal 1,2-epoxy group per molecule are reacted with a mercaptan and with an unsaturated monocarboxylic acid to form, on the average, vinyl ester compounds containing sulfide moieties after which said sulfide moieties are reacted with an alkylene oxide and a protonic acid to form sulfonium moieties of said vinyl ester compounds.

Claim 3

A process for preparing sulfonium-stabilized, water-compatible, radiation-curable vinyl ester resins wherein epoxy resins having on the average at least one pendant or terminal 1,2-epoxy group per molecule are reacted with a mercaptan and with an unsaturated monocarboxylic acid to form, on the average, vinyl ester resins containing sulfide moieties after which said sulfide moieties are reacted with an alkylene oxide and a protonic acid to form sulfonium moieties of said vinyl ester resins.

Claim 4

A process for preparing sulfonium-stabilized, water-compatible, radiation-curable vinyl ester resins wherein epoxy resins having on the average at least one pendant or terminal 1,2-epoxy group per molecule are reacted with a mercaptan and with an unsaturated monocarboxylic acid to form, on the average, vinyl ester resins containing sulfide moieties after which said sulfide moieties are reacted with an alkylene oxide and a protonic acid to form sulfonium moieties of said vinyl ester resins.

Claim 5

A process for preparing a sulfonium-stabilized, water-compatible, radiation-curable vinyl ester resins whereby molecules containing ester groups resulting from the esterification of an epoxy resin and an unsaturated monocarboxylic acid and molecules containing sulfonium groups and having the structure: ##STR8## wherein R 1 and R 2 are hydrocarbyl or inertly substituted hydrocarbyl groups of from 1 to 24 carbon atoms, and Z is the noncarboxylic portion of said unsaturated monocarboxylic acid when said ester is the monoester of a monoglycidyl ether, and Z is the noncarboxylic portion of a saturated or unsaturated monocarboxylic acid when said ester is a polyester of a polyglycidyl glycidyl ether whereby said resins are made by the process claimed in claim 2.

Claim 6

A process for preparing the sulfonium-stabilized vinyl ester resin as claimed in claim 2 wherein said unsaturated monocarboxylic acid is acrylic or methacrylic acid.

Claim 7

A process as claimed in claim 2 wherein said sulfonium moiety is a sulfonium acrylate or methacrylate.

Claim 8

A process as claimed in claim 2 wherein said vinyl ester resin is derived from an epoxy resin bearing, on the average, at least two vicinal epoxy groups per resin molecule.

Claim 9

A process as claimed in claim 2 wherein said epoxy resin bears, on the average, at least one glycidyl group per resin molecule.

Claim 10

A process for preparing the composition claimed in claim 2 wherein said epoxy resin corresponds to the formula: ##STR9## wherein R 1 and R 2 are hydrogen, lower alkyl of 1 to 6 carbon atoms, chlorine or bromine and m has an average numerical value of up to about 5; or ##STR10## wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen, lower alkyl of 1 to 6 carbon atoms, chlorine or bromine and --A-- is --S--, --O--, --S--S, ##STR11## or a divalent saturated hydrocarbon of from 1 to 6 carbon atoms and n has an average numerical value of up to about 12; or ##STR12## wherein R 5 and R 6 are each independently hydrogen or lower alkyl and n has a numerical value of up to 60.

Claim 11

A process for preparing the composition claimed in claim 2 wherein said epoxy resin corresponds to the formula: ##STR13## wherein R 1 and R 2 are hydrogen, lower alkyl of 1 to 6 carbon atoms, chlorine or bromine and m has an average numerical value of up to about 3; or ##STR14## wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen, lower alkyl of 1 to 6 carbon atoms, chlorine or bromine and --A-- is --S--, --O--, --S--S, ##STR15## or a divalent saturated hydrocarbon of from 1 to 6 carbon atoms and n has an average numerical value of up to about 3; or ##STR16## wherein R 5 and R 6 are each independently hydrogen or lower alkyl and n has a numerical value of up to 30.

Claim 12

A process as claimed in claim 8 wherein said vinyl ester bears acrylate or methacrylate moieties and wherein said sulfonium moiety is a sulfonium acrylate or methacrylate.

Claim 13

A process as claimed in claim 9 wherein said vinyl ester resin bears acrylate or methacrylate moieties and wherein said sulfonium moiety is a sulfonium acrylate or methacrylate.

Claim 14

A process as claimed in claim 2 wherein said preparation involves the reaction product of (1) a glycidyl ether with (2) about one equivalent of acrylic or methacrylic acid (3) from about 0.1 to about 0.8 equivalent or a mercaptan having a total carbon content of from 1 to about 12 carbon atoms and (4) from about 0.1 to about 0.8 equivalent of ethylene oxide.

Claim 15

A process as claimed in claim 12 wherein said glycidyl ether is (a) the diglycidyl ether of a polypropylene glycol having an epoxy equivalent weight of from about 94 to about 500 or (b) is the reaction product of epichlorohydrin with bisphenol-A having an epoxy equivalent weight of from about 170 to about 500 and wherein said mercaptan is 2-mercaptoethanol.

Claim 16

A process as claimed in claim 12 wherein said reaction product is combined with a diester of a diglycidyl ether and an unsaturated monocarboxylic acid.

Claim 17

A process as claimed in claim 2 wherein said unsaturated monocarboxylic acid has an acid dissociation constant of at least about 1×10 -7 .

Claim 18

A process as claimed in claim 2 wherein said unsaturated monocarboxylic acid has an acid dissociation constant of at least about 1×10 -5 .