Onium salts and the use thereof as photoinitiators

Claim 2

A composition of matter comprising a material curable by a Bronsted acid, and a sulfonium, selenonium, arsonium, ammonium or phosphonium salt comprising: a chromophore which absorbs visible radiation, said chromophore exhibiting a higher energy occupied molecular orbital than at least one other substituent attached to the S, Se, As, N or P atom of said salt; an insulating group which links said chromophore to the S, Se, As, N or P atom of said salt, said insulating group essentially preventing π resonance between said chromophore and the other substituents in said salt; at least one substituent comprising an electron withdrawing group and exhibiting a lower unoccupied molecular orbital than said chromophore; and, an anion; said salt being capable, upon exposure to visible radiation, of forming a Bronsted acid.

Claim 3

A composition of matter as defined in claim 1 wherein said salt is a sulfonium or arsonium salt which comprises: a chromophore which absorbs visible radiation, said chromophore (1) having a removable positive hydrogen ion and (2) exhibiting a higher energy occupied molecular orbital than at least one other substituent attached to the S or As atom of said salt; an insulating group which links said chromophore to the S or As atom of said salt, said insulating group essentially preventing π resonance between said chromophore and the other substituents in said salt; at least one substituent comprising an electron withdrawing group and exhibiting a lower unoccupied molecular orbital than said chromophore; and, an anion; said salt being capable, upon exposure to visible radiation, of forming, by an intramolecular rearrangement, a Bronsted acid comprising the anion of said salt and said removable hydrogen ion.

Claim 4

A composition of matter as defined in claim 2 wherein said salt is a sulfonium salt which comprises: a chromophore which absorbs visible radiation, said chromophore (1) having a removable positive hydrogen ion, and (2) exhibiting a higher energy occupied molecular orbital than at least one other substituent directly attached to the sulfur atom of said salt; an insulating group which links said chromophore to the sulfur atom of said salt, said insulating group essentially preventing π resonance between said chromophore and the other substituents in said salt; at least one substituent comprising an electron withdrawing group and exhibiting a lower unoccupied molecular orbital than said chromophore; and, an anion; said salt being capable, upon exposure to visible radiation, of forming, by an intramolecular rearrangement, a Bronsted acid comprising the anion of said salt and said removable hydrogen ion.

Claim 5

A composition of matter as defined in claim 1 wherein said salt has the following formula: ##STR12## wherein: R' represents an electron donating chromophore group which absorbs visible radiation, and which exhibits a higher energy occupied molecular orbital than at least one of R", R'" and R""; R" represents the same substituent as R' or R'", an optionally substituted aryl group or an optionally substituted alkyl group having from 1 to 18 carbon atoms; L represents a linking group which essentially prevents π resonance between R' and the remainder of the compound; R'" represents an electron withdrawing alkyl, aryl or heterocyclic group; J represents an S, Se, As, N or P atom; and when J represent As, N or P, R"" represents the same substituent as R', R" or R'" and, when J represents a S or Se atom, R"" represents O or an electron pair; and, W.sup.⊖ represents an anion capable of forming a Bronsted acid having a pKa of less than 7, said compound being capable, upon exposure to visible radiation of a wavelength absorbed by said chromophore, of forming a Bronsted acid.

Claim 6

A composition of matter as defined in claim 1 wherein said salt has the following formula: ##STR13## wherein: R' represents an electron donating chromophore group which absorbs visible radiation, has a removable positive hydrogen ion, and exhibits a higher energy occupied molecular orbital than at least one of R", R'" and R""; R" represents the same substituent as R' or R'", an optionally substituted aryl group or an optionally substituted alkyl group; L represents a linking group which essentially prevents π resonance between R' and the remainder of the compound; R'" represents an electron withdrawing alkyl, aryl or heterocyclic group; J represents a sulfur, selenium or arsenic atom; when J represents As, R"" represents the same substituent as R', R" or R'" and when J represents a sulfur or selnium atom, R"" represents O or an electron pair; and, W.sup.⊖ represents an anion capable of forming a Bronsted acid having a pKa of less than 7; said compound being capable, upon exposure to visible radiation of a wavelength absorbed by said chromophore, of forming, by intramolecular rearrangement, a Bronsted acid comprising W and said removable positive hydrogen of R'.

Claim 7

A composition of matter as defined in claim 1 wherein said salt has the following formula: ##STR14## wherein: R' represents an electron donating chromophore group which absorbs visible radiation, has a removable positive hydrogen ion, and exhibits a higher energy occupied molecular orbital than at least one of R", R'" and R""; R" represents the same substituent as R' or R'", an optionally substituted aryl group or an optionally substituted alkyl group; L represents a linking group which essentially prevents π resonance between R' and the remainder of the compound; R'" represents an electron withdrawing alkyl, aryl or heterocyclic group; J represents a sulfur atom; R"" represents O or an electron pair; and, W.sup.⊖ represents an anion capable of forming a Bronsted acid having a pKa of less than 7; said compound being capable, upon exposure to visible radiation of a wavelength absorbed by said chromophore, of forming, by intramolecular rearrangement, a Bronsted acid comprising W.sup.⊖ and said removable positive hydrogen of R'.

Claim 8

A composition of matter comprising a material curable by a Bronsted acid and a compound having the formula: ##STR15## wherein: R' represents one of the following chromophores: ##STR16## L represents one of the following linkages: ##STR17## wherein n represents 1 to 12; J, R", R'" and R"", taken together, represent one of the following groups: ##STR18## ##STR19## wherein Ar represents an optionally substituent aryl group; and W represents BF 4 , ClO 4 , AsF 6 , PF 6 , CF 3 SO 3 , CH 3 SO 3 , SnCl 4 , FeCl 4 , BiCl 4 or SbF 6 .

Claim 9

A composition of matter comprising a material curable by a Bronsted acid and a compound having the formula: ##STR15## wherein: R' represents one of the following chromophores: ##STR16## L represents one of the following linkages: ##STR17## wherein n represents 1 to 12; J, R", R'" and R"", taken together, represent one of the following groups: ##STR18## ##STR19## wherein Ar represents an optionally substituent aryl group; and W represents BF 4 , ClO 4 , AsF 6 , PF 6 , CF 3 SO 3 , CH 3 SO 3 , SnCl 4 , FeCl 4 , BiCl 4 or SbF 6 .

Claim 12

A method of curing as defined in claim 8 wherein said salt is a sulfonium or arsonium salt comprising: a chromophore which absorbs said visible radiation, said chromophore (1) having a removable positive hydrogen ion and (2) exhibiting a higher energy occupied molecular orbital than at least one other substituent directly attached to the S or As atom of said salt; an insulating group which links said chromophore to the S or As atom of said salt, said insulating group essentially preventing π resonance between said chromophore and the other substituents in said salt; at least one substituent comprising an electron withdrawing group and exhibiting a lower unoccupied molecular orbital than said chromophore; and, an anion; said salt being capable, upon exposure to said visible radiation, of forming, by an intramolecular rearrangement a Bronsted acid comprising the anion of said salt and said removable hydrogen ion.

Claim 13

A method of curing as defined in claim 8 wherein said salt is a sulfonium salt comprising: material curable by a Bronsted acid and (2) a sulfonium salt comprising: a chromophore which absorbs said visible radiation, said chromophore (1) having a removable positive hydrogen ion, and (2) exhibiting a higher energy occupied molecular orbital than at least one other substituent attached to the sulfur atom of said salt; an insulating group which links said chromophore to the sulfur atom of said salt, said insulating group essentially preventing π resonance between said chromophore and the other substituents in said salt; at least one substituent comprising an electron withdrawing group and exhibiting a lower unoccupied molecular orbital than said chromophore; and, an anion; said salt being capable, upon exposure to said visible radiation, of forming, by an intramolecular rearrangement, a Bronsted acid comprising the anion of said salt and said removable hydrogen ion.

Claim 14

A method of curing as defined in claim 8 wherein said salt has the following formula: ##STR20## wherein: R' represents an electron donating chromophore group which absorbs said visible radiation, has a removable positive hydrogen ion, and exhibits a higher energy occupied molecular orbital than at least one of R", R'" and R""; R" represents the same substituent as R' or R'", an optionally substituted aryl group or an optionally substituted alkyl group; L represents a linking group which essentially prevents π resonance between R' and the remainder of the compound; R'" represents an electron withdrawing alkyl, aryl or heterocyclic group; J represents a sulfur or arsonium atom; when J represents As, R"" represents the same substituent as R', R" or R'" and when J represents a sulfur atom, R"" represents O or an electron pair; and, W.sup.⊖ represents an anion capable of forming a Bronsted acid having a pKa of less than 7; said compound being capable, upon exposure to said visible radiation, of forming, by intramolecular rearrangement, a Bronsted acid comprising W and said removable positive hydrogen of R'.

Claim 15

A method of curing as defined in claim 8 wherein said salt has the following formula: ##STR21## wherein: R' represents an electron donating chromophore group which absorbs said visible radiation, has a removable positive hydrogen ion, and exhibits a higher energy occupied molecular orbital than at least one of R", R'" and R""; R" represents the same substituent as R' or R'", an optionally substituted aryl group or an optionally substituted alkyl group; L represents a linking group which essentially prevents π resonance between R' and the remainder of the compound; R'" represents an electron withdrawing alkyl, aryl or heterocyclic group; J represents a sulfur atom; R"" represents O or an electron pair; and, W.sup.⊖ represents an anion capable of forming a Bronsted acid having a pKa of less than 7; said compound being capable, upon exposure to said visible radiation, of forming, by intramolecular rearrangement, a Bronsted acid comprising W.sup.⊖ and said removable positive hydrogen of R'.

Claim 16

A method of curing as defined in claim 8 wherein said salt has the following formula: material curable by a Bronsted acid and (2) a compound having the formula: ##STR22## wherein: R' represents one of the following chromophores: ##STR23## L represents one of the following linkages: ##STR24## wherein n represents 1 to 12; J, R", R'" and R"", taken together, represent one of the following groups: ##STR25## wherein Ar represents an optionally substituent aryl group and alkyl represents an alkyl group from C 1 to C 10 ; and W.sup.⊖ represents BF 4 , ClO 4 , AsF 6 , PF 6 , CF 3 SO 3 , CH 3 SO 3 , SnCl 4 , FeCl 4 , BiCl 4 or SbF 6 .

Claim 19

A composition of matter comprising a material curable by a Bronsted acid and a salt having the following formula: ##STR27## wherein: R' represents an electron donating chromophore group which absorbs visible radiation, and which exhibits a higher energy occupied molecular orbital than at least one of R", R'" and R""; R" represents the same substitutent as R' or R'", an optionally substituted aryl group or an optionally substituted alkyl group having from 1 to 18 carbon atoms; L represents orthophenylene; R'" represents an electron withdrawing alkyl, aryl or heterocyclic group; J represents an S, Se, As, N or P atom; and when J represent As, N or P, R"" represents the same substituent as R', R" or R'" and, when J represents a S or Se atom, R"" represents O or an electron pair; and, W.sup.⊖ represents an anion capable of forming a Bronsted acid having a pKa of less than 7, said compound being capable, upon exposure to visible radiation of a wavelength absorbed by said chromophore, of forming a Bronsted acid.

Claim 20

A composition of matter comprising a material curable by a Bronsted acid and a salt having the following formula: ##STR27## wherein: R' represents an electron donating chromophore group which absorbs visible radiation, and which exhibits a higher energy occupied molecular orbital than at least one of R", R'" and R""; R" represents the same substitutent as R' or R'", an optionally substituted aryl group or an optionally substituted alkyl group having from 1 to 18 carbon atoms; L represents orthophenylene; R'" represents an electron withdrawing alkyl, aryl or heterocyclic group; J represents an S, Se, As, N or P atom; and when J represent As, N or P, R"" represents the same substituent as R', R" or R'" and, when J represents a S or Se atom, R"" represents O or an electron pair; and, W.sup.⊖ represents an anion capable of forming a Bronsted acid having a pKa of less than 7, said compound being capable, upon exposure to visible radiation of a wavelength absorbed by said chromophore, of forming a Bronsted acid.

Claim 21

A composition of matter as defined in claim 15 wherein said salt has the formula: ##STR28## wherein: R' represents one of the following chromophores: ##STR29## L represents: ##STR30## J, R", R'" and R"", taken together, represent one of the following groups: ##STR31## wherein Ar represents an optionally substituent aryl group; and W.sup.⊖ represents BF 4 , ClO 4 , AsF 6 , PF 6 , CF 3 SO 3 , CH 3 SO 3 , SnCl 4 , FeCl 4 , BiCl 4 or SbF 6 .