Photopolymerizable composition containing ethylenically unsaturated oligomers

Claim 2

A photopolymerizable composition comprising (1) 10% to 60% by weight of an oligomer of the formula ##STR14## wherein E is an ethylenically unsaturated, free radical polymerizable group, D is the residue of a polyisocyanate having at least two of its isocyanate groups reacted to form ##STR15## groups bonded to E and R, R is the residue of a polyol having at least a +b hydroxyl groups, the residue formed by removal of hydrogen from the hydroxyl groups, said polyol having a number average molecular weight between 90 and 10,000, A is a carboxylic acid containing group, a is a number having an average value between 2 and 20, and b is a number having an average value between 0.3 and 10, (2) 10% to 60% by weight of an organic film forming polymer having a molecular weight of at least 6,000, (3) 10% to 60% by weight of a free radical polymerizable monomer having at least one ethylenically unsaturated group, and (4) 0.1% to 12% by weight of a photoinitiator system capable of initiating free radical polymerization upon absorption of electromagnetic radiation.

Claim 3

The photopolymerizable composition of claim 1 wherein E is selected from the class consisting of acryloyloxyalkoxy, methacryloyloxyalkoxy, vinylalkoxy, and allyloxy groups, D is the residue of a diisocyanate, A is selected from the group consisting of ##STR16## and m is an integer of from 1 to 6 inclusive.

Claim 4

The photopolymerizable composition of claim 2 wherein E is selected from the class consisting of acryloyloxyalkoxy and methacryloyloxyalkoxy, and said free radical polymerizable monomer has 2 to 4 ethylenically unsaturated groups selected from the class consisting of acryloxy and methacryloxy.

Claim 5

The photopolymerizable composition of claim 3 wherein R is the residue of a polyesterpolyol having a hydroxy equivalent weight between 90 and 4,000.

Claim 6

The photopolymerizable composition of claim 4 wherein said film forming polymer is selected from the group consisting of polyvinyl acetals, polyvinylalcohol, polyvinylpyrolidone, polyamides, hydroxyalkylecelluloses, polyvinylacetate, and copolymers of polyvinylchloride and polyvinylacetate.

Claim 7

The photopolymerizable system of claim 3 wherein said photoinitiator system comprises an initiator from the class consisting of aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic diazonium salts, biimidazoles, and chloroalkyl triazines.

Claim 8

The photopolymerizable system of claim 4 wherein said photoinitiator system comprises an initiator from the class consisting of aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic diazonium salts, biimidazoles, and chloroalkyl triazines.

Claim 9

The photopolymerizable system of claim 5 wherein said photoinitiator system comprises an initiator from the class consisting of aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic diazonium salts, biimidazoles, and chloroalkyl triazines.

Claim 10

The photopolymerizable composition of claim 1 further comprising 10 to 96% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 11

The photopolymerizable composition of claim 3 further comprising 10 to 96% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 12

The photopolymerizable composition of claim 4 further comprising 10 to 96% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 13

The photopolymerizable composition of claim 6 further comprising 10 to 96% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 14

The photopolymerizable composition of claim 8 further comprising 10 to 96% by weight of a solvent which is not reactive with carboxyl grups or ethylenically unsaturated groups.

Claim 15

The photopolymerizable composition of claim 4 further comprising 85 to 95% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 16

The photopolymerizable composition of claim 5 further comprising 85 to 95% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 17

The photopolymerizable composition of claim 6 further comprising 85 to 95% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 18

The photopolymerizable composition of claim 8 further comprising 85 to 95% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 19

the photopolymerizable composition of claim 4 further comprising 15 to 45% by weight of oligomer,

Claim 20

15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 21

15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 22

The photopolymerizable composition of claim 5 further comprising 15 to 45% by weight of oligomer, 15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 23

The photopolymerizable composition of claim 6 further comprising 15 to 45% by weight of oligomer, 15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 24

The photopolymerizable composition of claim 9 further comprising 15 to 45% by weight of oligomer, 15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 25

The photopolymerizable composition of claim 14 further comprising 15 to 45% by weight of oligomer, 15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 26

The photopolymerizable composition of claim 1 wherein said oligomer is represented by the formula: ##STR17## wherein E is an ethylenically unsaturated free radical polymerizable group selected from acryloyloxyalkoxy and methacryloyloxyalkoxy, D is the residue of a diisocyanate having its two isocyanate groups reacted to form ##STR18## groups bonded to E and R 1 , R 1 is the residue formed by the removal of active hydrogen atoms and hydroxyl groups from oligomeric Ω-hydroxy carboxylic acids or the residue formed by the removal of active hydrogen atoms and hydroxyl groups from oligomeric diols, R 2 is the residue of an aliphatic polyol having the formula R 5 (OH) a+b after removal of a+b hydrogens from hydroxyl groups and having a valence of a+b, or the residue of an aliphatic polyol having the formula ##EQU1## after removal of (a+b-1) hydrogens from hydroxyl groups and R 5 is the residue of an aliphatic polyol radical formed by having the OH groups of the polyol removed therefrom and having 3 to 10 valences substituted with OH groups, R 3 is the residue formed by removal of two ##STR19## groups from a dicarboxylic acid, a is a number having an average value of from 2 to 20, and b is a number having an average value of from 0.3 to 10, wherein the molecular weight of (R 1 ) a R 2 (R 1 ) b is between 200 and 5,000.

Claim 27

The photopolymerizable composition of claim 23 further comprising 15 to 45% by weight of oligomer, 15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polyermizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 28

The photopolymerizable composition of claim 23 further comprising 85 to 95% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 29

The photopolymerizable composition of claim 23 wherein said film forming polymer is a polyvinyl acetal.

Claim 30

The photopolymerizable composition of claim 24 wherein said film forming polymer is a polyvinyl acetal.

Claim 31

The photopolymerizable composition of claim 25 wherein said film forming polymer is a polyvinyl acetal.

Claim 32

The photopolymerizable composition of claim 1 wherein said oligomer is represented by the formula: ##STR20## wherein R 3 is the residue formed by the removal of two ##STR21## groups from a dicarboxylic acid, R 4 is H or CH 3 , c is 2 to 5 inclusive, p is a number average value of from 2 to 7.7, q is a number average value of from 0.3 to 4, R 6 is the residue formed by the removal of two isocyanate groups from a diisocyanate, and R 7 is an organic radical which is the residue of an organic polyol with at least three hydroxyl groups removed therefrom and having a molecular weight of from 90 to 10,000.

Claim 33

The photopolymerizable composition of claim 29 wherein said film forming polymer is a polyvinyl acetal.

Claim 34

The photopolymerizable composition of claim 29 further comprising 85 to 95% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 35

The photopolymerizable composition of claim 30 further comprising 85 to 95% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 36

The photopolymerizable compositions of claim 29 further comprising 15 to 45% by weight of oligomer, 15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 37

the photopolymerizable composition of claim 32 further comprising 15 to 45% by weight of oligomer, 15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 38

The photopolymerizable system of claim 29 wherein said photoinitiator system comprises an initiator from the class consisting of aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic diazonium salts, biimidazoles, and chloroalkyl triazines.

Claim 39

The photopolymerizable system of claim 32 wherein said photoinitiator system comprises an initiator from the class consisting of aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic diazonium salts, biimidazoles, and chloroalkyl triazines.

Claim 40

The photopolymerizable system of claim 34 wherein said photoinitiator system comprises an initiator from the class consisting of aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic diazonium salts, biimidazoles, and chloroalkyl triazones.

Claim 41

The photopolymerizable composition of claim 1 wherein said oligomer is of the formula ##STR22## wherein R 3 is the residue formed by removal of two ##STR23## groups from a dicarboxylic acid, R 4 is H or CH 3 , R 6 and R 8 are independently the residues formed by the removal of two isocyanate groups from a diisocyanate, d is 1 to 6 inclusive, e is an average value of 0.5 to 5 inclusive R 9 is an alkanepolyyl radical having a valence of h+l that is the residue of an alkanepolyol having h+l hydroxyl groups removed therefrom, said alkanepolyol having a molecular weight of from 100 to 10,000, f is an integer of 1 to 6, and h is a integer of 2 to 8.

Claim 42

The photopolymerizable composition of claim 38 wherein said film forming polymer is a polyvinyl acetal.

Claim 43

The photopolymerizable composition of claim 38 further comprising 85 to 95% by weight of a solvent which is not reactive with carboxyl groups or ethylenically unsaturated groups.

Claim 44

The photopolymerizable composition of claim 38 further comprising 15 to 45% by weight of oligomer, 15 to 35% by weight of organic film forming polymer, 25 to 50% by weight of free radical polymerizable monomer, and a photoinitiator system comprising in parts by weight of the polymerizable composition 2 to 8% of initiator and 1 to 4% photosensitizer.

Claim 45

The photopolymerizable system of claim 38 wherein said photoinitiator system comprises an initiator from the class consisting of aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic diazonium salts, biimidazoles, and chloroalkyl triazines.

Claim 46

The photopolymerizable system of claim 40 wherein said photoinitiator system comprises an initiator from the class consisting of aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic diazonium salts, biimidazoles, and chloroalkyl triazones.

Claim 47

The photopolymerizable composition of claim 40 wherein said film forming polymer is a polyvinyl acetal.

Claim 48

The photopolymerizable composition of claim 35 wherein said film forming polymer is a polyvinyl acetal.

Claim 49

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 1.

Claim 50

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 4.

Claim 51

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 5.

Claim 52

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 3 of the photopolymerizable composition of claim 6.

Claim 53

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 18.

Claim 54

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 23.

Claim 55

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 24.

Claim 56

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerization composition of claim 33.

Claim 57

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 35.

Claim 58

A presensitized plate comprising a grained and anodized aluminum substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 38.

Claim 59

The plate of claim 48 having an oxygen barrier layer comprising an organic polymer which is soluble in an aqueous alkaline solution of pH 8-13 coated over the photopolymerizable composition.

Claim 60

The plate of claim 50 having an oxygen barrier layer comprising an organic polymer which is soluble in an aqueous alkaline solution of pH 8-13 coated over the photopolymerizable composition.

Claim 61

The plate of claim 52 having an oxygen barrier layer comprising an organic polymer which is soluble in an aqueous alkaline solution of pH 8-13 coated over the photopolymerizable composition.

Claim 62

The plate of claim 54 having an oxygen barrier layer comprising an organic polymer which is soluble in a aqueous alkaline solution of pH 8-13 coated over the photopolymerizable composition.

Claim 63

The plate of claim 56 having an oxygen barrier layer comprising an organic polymer which is soluble in an aqueous alkaline solution of pH 8-13 coated over the photopolymerizable composition.

Claim 64

A presensitized plate comprising a substrate coated with 0.3 to 9 grams/m 2 of the photopolymerizable composition of claim 1.

Claim 65

The composition of claim 1 wherein a is 3 or 4.

Claim 66

The composition of claim 2 wherein a is 3 or 4.

Claim 67

The composition of claim 3 wherein a is 3 or 4.

Claim 68

The composition of claim 18 wherein a is 3 or 4.

Claim 69

The composition of claim 21 wherein a is 3 or 4.

Claim 70

The composition of claim 23 wherein a is 3 or 4.

Claim 71

The composition of claim 29 wherein p is selected from 3 and 4.