Sulfonate-containing photopolymer systems

Claim 2

A sulfocompound which is the poly(ethylenically-unsaturated ester or amide) of a sulfopolyol or sulfopolyamine comprising the reaction product of: a. a sulfopolyol or sulfopolyamine which is the reaction product of (1) one mole of a sulfodicarboxylic acid and (2) two moles of an aliphatic polyol or polyamine having two or more hydroxyl or amine groups attached to a saturated linear chain of up to about 55 carbon atoms in units of 2 to 12 --CH 2 -- groups separated by 0 to 22 --O-- atoms and 0 to 8 ##STR15## groups, the polyol and polyamine having a molecular weight of less than 1000 and (c+1) hydroxyl or amino groups (in which c is an integer of 1, 2, or 3); and b. 2 c moles of either (1), (2), or (3), in which (1) is a compound selected from (a) 2-alkenylazlactones having the formula ##STR16## wherein R is hydrogen or methyl; R 1 is a covalent bond, --CH 2 -- or --CH 2 CH 2 --, R 2 and R 3 are independently hydrogen or methyl; and (b) ethylenically-unsaturated isocyanates having the formula ##STR17## wherein R 4 is a covalent bond, --CH 2 --, ##STR18## wherein R 5 is a linear or branched chain of 1 to 12 carbon atoms which can contain one catenary oxygen atom or ##STR19## group or R 5 is a 5- or 6-membered carbocyclic group which is unsubstituted or substituted by lower alkyl groups having 1 to 4 carbon atoms, the carbocyclic group having a total of up to 12 carbon atoms, and R 6 is an organic group selected from linear or branched alkylene groups having 2 to 12 carbon atoms, a cyclopentamethylene group, a cyclohexamethylene group, a 5- or 6-membered azacyclic group, a phenylene group, a naphthalene group, a phenylenemethylenephenylene group, the organic group being unsubstituted or substituted by up to four lower alkyl groups having 1 to 4 carbon atoms and a total of up to 15 carbon atoms; or (2) a diisocyanate having the formula OCN--R.sup.6 --NCO, III the reaction product of said sulfopolyester polyol and said diisocyanate then being reacted with 2 c moles of an ethylenically-unsaturated alcohol having the formula ##STR20## wherein R and R 6 are as defined above; R 7 is ##STR21## R 8 is a polyvalent aliphatic group selected from linear and branched alkyl groups having a valence of (a+1), 2 to 12 carbon atoms which can contain one nonperoxidic catenary oxygen atom or one ##STR22## group, and alicyclic groups having a 5- or 6-atom carbocyclic structure which is unsubstituted or substituted by up to 4 lower alkyl groups having 1 to 4 carbon atoms and a total of up to 12 carbon atoms; and a is an integer of 1, 2, or 3; or (3) the reaction product of one mole of organic diisocyanate of Formula III and one mole of an ethylenically-unsaturated alcohol of Formula IV; there being essentially no hydroxyl, amino, or isocyanate groups remaining after the reaction of a. with b. (1), b.(2), or b.(3), and the sulfocompound contains a single central sulfo group.

Claim 3

The sulfocompound according to claim 1 wherein said polyol is selected from the reaction product of one mole of 5-sulfoisophthalic acid and two moles of a polyol selected from the group consisting of poly(oxytetramethylene)diol, poly(oxyethylene)glycol, polycaprolactonepolyol, and pentaerythritol.

Claim 4

The sulfocompound according to claim 1 wherein said dicarboxylic acid is selected from 5-sulfoisophthalic acid, 3-sulfoglutaric acid, and sulfosuccinic acid.

Claim 5

The sulfocompound according to claim 1 wherein said polyamine is selected from polyoxypropylene di- and triamines and polyoxyethylene di- and triamines.

Claim 6

The sulfocompound having a formula selected from ##STR23## wherein: R is hydrogen or methyl; R 6 is an organic group selected from linear or branched alkylene groups having 2 to 12 carbon atoms, a cyclopentamethylene group, a cyclohexamethylene group, a 5- or 6-membered azacyclic group, a phenylene group, a naphthalene group, a phenylenemethylenephenylene group, the organic group being unsubstituted or substituted by up to four lower alkyl groups having 1 to 4 carbon atoms and a total of up to 15 carbon atoms; R 7 is ##STR24## R 8 is a polyvalent aliphatic group selected from linear and branched alkyl groups having a valence of (a+1), 2 to 12 carbon atoms which can contain one nonperoxidic catenary oxygen atom or one ##STR25## group, and alicyclic groups having a 5-or 6-atom carboxylic structure which is unsubstituted or substituted by up to 4 lower alkyl groups having 1 to 4 carbon atoms and a total of up to 12 carbon atoms; c is an integer of 1, 2, or 3; R 9 is an arenetriyl group (trivalent arene group) having 6 to 12 carbon atoms or an alkanetriyl (trivalent alkane group) group having 2 to 12 carbon atoms remaining after the removal of carboxyl and sulfo groups from sulfoarene- and sulfoalkane dicarboxylic acids having the formula ##STR26## in which M is a cation; R 1O is a linear aliphatic group having a valence of (c+1) consisting of a saturated chain of up to about 55 carbon atoms in units of 2 to 12 --CH 2 -- groups separated by 0 to 22 --O-- atoms and 0 to 8 ##STR27## groups, the aliphatic group having a molecular weight of less than 1000, wherein c is an integer having a value of 1, 2, or 3; R 11 is ##STR28## in which R 1 is a covalent bond, --CH 2 -- or --CH 2 CH 2 --, R 2 and R 3 are independently hydrogen or methyl; R 4 is a covalent bond, --CH 2 --, ##STR29## wherein R 5 is a linear or branched chain of 1 to 12 carbon atoms which can contain one catenary oxygen atom or ##STR30## group or R 5 is a 5- or 6-membered carbocylic group which is unsubstituted or substituted by lower alkyl groups having 1 to 4 carbon atoms, the carbocyclic group having a total of up to 12 carbon atoms, R 6 is as defined above, X is --O-- or --NH--; and a is an integer having a value of 1, 2, or 3.

Claim 7

The sulfocompound having a formula selected from ##STR23## wherein: R is hydrogen or methyl; R 6 is an organic group selected from linear or branched alkylene groups having 2 to 12 carbon atoms, a cyclopentamethylene group, a cyclohexamethylene group, a 5- or 6-membered azacyclic group, a phenylene group, a naphthalene group, a phenylenemethylenephenylene group, the organic group being unsubstituted or substituted by up to four lower alkyl groups having 1 to 4 carbon atoms and a total of up to 15 carbon atoms; R 7 is ##STR24## R 8 is a polyvalent aliphatic group selected from linear and branched alkyl groups having a valence of (a+1), 2 to 12 carbon atoms which can contain one nonperoxidic catenary oxygen atom or one ##STR25## group, and alicyclic groups having a 5-or 6-atom carboxylic structure which is unsubstituted or substituted by up to 4 lower alkyl groups having 1 to 4 carbon atoms and a total of up to 12 carbon atoms; c is an integer of 1, 2, or 3; R 9 is an arenetriyl group (trivalent arene group) having 6 to 12 carbon atoms or an alkanetriyl (trivalent alkane group) group having 2 to 12 carbon atoms remaining after the removal of carboxyl and sulfo groups from sulfoarene- and sulfoalkane dicarboxylic acids having the formula ##STR26## in which M is a cation; R 1O is a linear aliphatic group having a valence of (c+1) consisting of a saturated chain of up to about 55 carbon atoms in units of 2 to 12 --CH 2 -- groups separated by 0 to 22 --O-- atoms and 0 to 8 ##STR27## groups, the aliphatic group having a molecular weight of less than 1000, wherein c is an integer having a value of 1, 2, or 3; R 11 is ##STR28## in which R 1 is a covalent bond, --CH 2 -- or --CH 2 CH 2 --, R 2 and R 3 are independently hydrogen or methyl; R 4 is a covalent bond, --CH 2 --, ##STR29## wherein R 5 is a linear or branched chain of 1 to 12 carbon atoms which can contain one catenary oxygen atom or ##STR30## group or R 5 is a 5- or 6-membered carbocylic group which is unsubstituted or substituted by lower alkyl groups having 1 to 4 carbon atoms, the carbocyclic group having a total of up to 12 carbon atoms, R 6 is as defined above, X is --O-- or --NH--; and a is an integer having a value of 1, 2, or 3.

Claim 8

The sulfocompound according to claim 5 wherein R 4 is ##STR31## R 10 is derived from a polycaprolactonepolyol or polyoxyalkylene-polyol having a molecular weight of up to 1000, and R 9 is an arenetriyl group.

Claim 9

The sulfocompound according to claim 5 wherein said diisocyanate from which R 6 is derived is selected from toluene diisocyanate, isophorone diisocyanate, and bis(4-isocyanatophenyl)methane.

Claim 10

The sulfocompound according to claim 5 in which R 8 is a group selected from ##STR32## wherein e is an integer of 1 to 4 inclusively.

Claim 11

The sulfocompound according to claim 1, wherein R 8 is selected from ##STR33##

Claim 12

A sulfocompound which is the poly(ethylenically-unsaturated ester or amide) of a sulfopolyol or sulfopolyamine comprising the reaction product of: a. a sulfopolyol or sulfopolyamine which is the reaction product of (1) one mole of a sulfodicarboxylic acid and (2) two moles of an aliphatic polyol or polyamine having two or more hydroxyl or amine groups attached to a saturated linear chain of up to about 55 carbon atoms in units of 2 to 12 --CH 2 -- groups separated by 0 to 22 --O-- atoms and 0 to 8 ##STR34## groups, the polyol and polyamine having a molecular weight of less than 1000 and (c+1) hydroxyl or amino groups (in which c is an integer of 1, 2, or 3); and b. 2 c moles of either (1), (2), or (3), in which (1) is a compound selected from (a) 2-alkenylazlactones having the formula ##STR35## wherein R is hydrogen or methyl; R 1 is a covalent bond, --CH 2 -- or --CH 2 CH 2 --, R 2 and R 3 are independently hydrogen or methyl; and (b) ethylenically-unsaturated isocyanates having the formula ##STR36## wherein R 4 is a covalent bond, --CH 2 --, ##STR37## wherein R 5 is a linear or branched chain of 1 to 12 carbon atoms which can contain one catenary oxygen atom or ##STR38## group or R 5 is a 5- or 6-membered carbocyclic group which is unsubstituted or substituted by lower alkyl groups having 1 to 4 carbon atoms, the carbocyclic group having a total of up to 12 carbon atoms, and R 6 is an organic group selected from linear or branched alkylene groups having 2 to 12 carbon atoms, a cyclopentamethylene group, a cyclohexamethylene group, a 5- or 6-membered azacyclic group, a phenylene group, a naphthalene group, a phenylenemethylenephenylene group, the organic group being unsubstituted or substituted by up to four lower alkyl groups having 1 to 4 carbon atoms and a total of up to 15 carbon atoms; or (2) a diisocyanate having the formula OCN--R.sup.6 --NCO, III the reaction product of said sulfopolyester polyol and said diisocyanate then being reacted with 2 c moles of an ethylenically-unsaturated alcohol having the formula ##STR39## wherein R and R 6 are as defined above; R 7 is ##STR40## R 8 is a polyvalent aliphatic group selected from linear and branched alkyl groups having a valence of (a+1), 2 to 12 carbon atoms which can contain one nonperoxidic catenary oxygen atom or one ##STR41## group, and alicyclic groups having a 5- or 6-atom carbocyclic structure which is unsubstituted or substituted by up to 4 lower alkyl groups having 1 to 4 carbon atoms and a total of up to 12 carbon atoms, and a is an integer of 1, 2, or 3; or (3) the reaction product of one mole of organic diisocyanate of Formula III and one mole of an ethylenically-unsaturated alcohol of Formula IV; providing that at least one of a and c is equal to 2 or 3, and there being essentially no hydroxyl, amino, or isocyanate groups remaining after the reaction of a. with b.(1), b.(2), or b.(3).

Claim 13

A sulfocompound which is the poly(ethylenically-unsaturated ester or amide) of a sulfopolyol or sulfopolyamine comprising the reaction product of: a. a sulfopolyol or sulfopolyamine which is the reaction product of (1) one mole of a sulfodicarboxylic acid and (2) two moles of an aliphatic polyol or polyamine having two or more hydroxyl or amine groups attached to a saturated linear chain of up to about 55 carbon atoms in units of 2 to 12 --CH 2 -- groups separated by 0 to 22 --O-- atoms and 0 to 8 ##STR34## groups, the polyol and polyamine having a molecular weight of less than 1000 and (c+1) hydroxyl or amino groups (in which c is an integer of 1, 2, or 3); and b. 2 c moles of either (1), (2), or (3), in which (1) is a compound selected from (a) 2-alkenylazlactones having the formula ##STR35## wherein R is hydrogen or methyl; R 1 is a covalent bond, --CH 2 -- or --CH 2 CH 2 --, R 2 and R 3 are independently hydrogen or methyl; and (b) ethylenically-unsaturated isocyanates having the formula ##STR36## wherein R 4 is a covalent bond, --CH 2 --, ##STR37## wherein R 5 is a linear or branched chain of 1 to 12 carbon atoms which can contain one catenary oxygen atom or ##STR38## group or R 5 is a 5- or 6-membered carbocyclic group which is unsubstituted or substituted by lower alkyl groups having 1 to 4 carbon atoms, the carbocyclic group having a total of up to 12 carbon atoms, and R 6 is an organic group selected from linear or branched alkylene groups having 2 to 12 carbon atoms, a cyclopentamethylene group, a cyclohexamethylene group, a 5- or 6-membered azacyclic group, a phenylene group, a naphthalene group, a phenylenemethylenephenylene group, the organic group being unsubstituted or substituted by up to four lower alkyl groups having 1 to 4 carbon atoms and a total of up to 15 carbon atoms; or (2) a diisocyanate having the formula OCN--R.sup.6 --NCO, III the reaction product of said sulfopolyester polyol and said diisocyanate then being reacted with 2 c moles of an ethylenically-unsaturated alcohol having the formula ##STR39## wherein R and R 6 are as defined above; R 7 is ##STR40## R 8 is a polyvalent aliphatic group selected from linear and branched alkyl groups having a valence of (a+1), 2 to 12 carbon atoms which can contain one nonperoxidic catenary oxygen atom or one ##STR41## group, and alicyclic groups having a 5- or 6-atom carbocyclic structure which is unsubstituted or substituted by up to 4 lower alkyl groups having 1 to 4 carbon atoms and a total of up to 12 carbon atoms, and a is an integer of 1, 2, or 3; or (3) the reaction product of one mole of organic diisocyanate of Formula III and one mole of an ethylenically-unsaturated alcohol of Formula IV; providing that at least one of a and c is equal to 2 or 3, and there being essentially no hydroxyl, amino, or isocyanate groups remaining after the reaction of a. with b.(1), b.(2), or b.(3).

Claim 14

The sulfocompound which is the reaction product of: a. a sulfopolyol which is the reaction product of (1) 1 mole of dimethyl 5-sulfoisophthalate, and (2) 2 moles of polycaprolactonediol, and b. 2 moles of bis(4-isocyanatophenyl)methane; the reaction product of a. and b. then being reacted with 2 moles of pentaerylthrytol triacrylate.

Claim 15

The sulfocompound which is the reaction product of: a. a sulfopolyol which is the reaction product of (1) 1 mole of dimethyl 5-sulfoisophthalate, and (2) 2 moles of polycaprolactonediol, and b. 2 moles of bis(4-isocyanatophenyl)methane; the reaction product of a. and b. then being reacted with 2 moles of pentaerylthrytol triacrylate.