US5147758A — Red sensitive photopolymerizable compositions

Claim 1

Independent Claim 333 words

A photopolymerizable composition comprising: (A) an ethylenically unsaturated monomer; and (B) an initiator system, said initiator system comprising: (1) a squarylium compound selected from the group consisting of: ##STR15## wherein: R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, hydroxyl, halogen, alkyl of one to six carbon atoms, or substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; R 5 , R 7 , and R 8 are each independently hydrogen, a substituted or unsubstituted alkyl or cycloalkyl group having from 1 to 6 carbon atoms or a substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; or any of R 1 , R 2 , R 3 , and R 4 groups are combined with any of R 5 , R 6 , R 7 , and R 8 and/or with each other to a form a 5- to 7-membered substituted or unsubstituted carbocyclic or heterocyclic ring; or any of R 5 , R 6 , R 7 , and R 8 are joined together to form a 5- to 7-membered substituted or unsubstituted nitrogen-containing heterocyclic ring; and n and m are each independently 1 to 3; and ##STR16## wherein X and Y are each independently oxygen or sulfur and R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently alkyl groups from one to eight carbon atoms; and (2) a borate salt containing (a) an alkali metal cation or a quarternary ammonium cation and (b) a borate anion container represented by the formula: (BZ.sup.1 Z.sup.2 Z.sup.3 Z.sup.4).sup.-- wherein Z 1 , Z 2 , Z 3 , and Z 4 , the same or different, are selected from the group consisting of alkyl, aryl, aralkyl, alkenyl, alkynyl, alicyclic, heterocyclic, and allyl groups, with the proviso that at least one of Z 1 , Z 2 , Z 3 , and Z 4 is not aryl.

Claim 2

Dependent Claim 333 words

A photopolymerizable composition comprising: (A) an ethylenically unsaturated monomer; and (B) an initiator system, said initiator system comprising: (1) a squarylium compound selected from the group consisting of: ##STR15## wherein: R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, hydroxyl, halogen, alkyl of one to six carbon atoms, or substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; R 5 , R 7 , and R 8 are each independently hydrogen, a substituted or unsubstituted alkyl or cycloalkyl group having from 1 to 6 carbon atoms or a substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; or any of R 1 , R 2 , R 3 , and R 4 groups are combined with any of R 5 , R 6 , R 7 , and R 8 and/or with each other to a form a 5- to 7-membered substituted or unsubstituted carbocyclic or heterocyclic ring; or any of R 5 , R 6 , R 7 , and R 8 are joined together to form a 5- to 7-membered substituted or unsubstituted nitrogen-containing heterocyclic ring; and n and m are each independently 1 to 3; and ##STR16## wherein X and Y are each independently oxygen or sulfur and R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently alkyl groups from one to eight carbon atoms; and (2) a borate salt containing (a) an alkali metal cation or a quarternary ammonium cation and (b) a borate anion container represented by the formula: (BZ.sup.1 Z.sup.2 Z.sup.3 Z.sup.4).sup.-- wherein Z 1 , Z 2 , Z 3 , and Z 4 , the same or different, are selected from the group consisting of alkyl, aryl, aralkyl, alkenyl, alkynyl, alicyclic, heterocyclic, and allyl groups, with the proviso that at least one of Z 1 , Z 2 , Z 3 , and Z 4 is not aryl.

Claim 3

Dependent Claim 9 words

The composition of claim 1 additionally comprising a binder.

Claim 4

Dependent Claim 145 words

The composition of claim 2 wherein said squarylium compound is selected from the group consisting of: ##STR17## wherein; R 2 is hydrogen or substituted or unsubstituted alkyl; R 5 is (1) substituted or unsubstituted alkyl or cycloalkyl having from 1 to 6 carbon atoms or (2) substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; or R 2 and R 5 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring; Q is O, S, Se, NR 40 , or CR 41 R 42 , where R 40 , R 41 , and R 42 are each independently alkyl of 1 to 6 carbon atoms or substituted or unsubstituted phenyl; R 15 and R 16 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic or heterocyclic ring; and m is 1 or 2.

Claim 5

Dependent Claim 268 words

The composition of claim 3 wherein said squarylium compound is selected from the group consisting of: ##STR18## wherein R 2 and R 3 are each independently hydrogen or substituted or unsubstituted alkyl; R 5 and R 7 are each independently (1) substituted or unsubstituted alkyl or cycloalkyl having from 1 to 6 carbon atoms or (2) substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; or R 2 and R 5 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring; and R 3 and R 7 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring; Q and T are each independently 0, S, Se, NR 40 , or CR 41 R 42 , where R 40 , R 41 , and R 42 are each independently alkyl of 1 to 6 carbon atoms or substituted or unsubstituted phenyl; R 17 , R 18 , R 19 , R 20 , R 21 , R 22 R 38 , and R 39 are each independently hydrogen, halogen, dialkylamino, substituted or unsubstituted phenyl, substituted or unsubstituted alkyl, alkoxyl, or cycloalkyl having from 1 to 6 carbon atoms; or (R 38 and R 17 ), (R 17 and R 18 ), or (R 18 and R 19 ) are joined in a substituted or unsubstituted aromatic ring containing 5 to 7 atoms; and, independently, (R 39 and R 20 ), (R 20 and R 21 ), or (R 21 and R 22 ) are joined in a substituted or unsubstituted aromatic ring containing 5 to 7 atoms.

Claim 6

Dependent Claim 20 words

The composition of claim 4 wherein Q and T are the same and equal to CR 41 R 42 .

Claim 7

Dependent Claim 73 words

The composition of claim 5 wherein R 41 and R 42 are the same and equal to methyl, R 5 and R 7 are the same and equal to methyl or ethyl; R 17 , R 19 , R 20 , R 22 , R 38 , and R 39 are the same and equal to hydrogen; and R 18 and R 21 are the same and equal to hydrogen, chloro, or methoxyl.

Claim 8

Dependent Claim 31 words

The composition of claim 6 wherein R 5 and R 7 are the same and equal to methyl and R 18 and R 21 are the same and equal to hydrogen.

Claim 9

Dependent Claim 75 words

The composition of claim 5 wherein R 41 and R 42 are the same and equal to methyl, R 17 , R 20 , R 38 , and R 39 are the same and equal to hydrogen, (R 18 and R 19 ) and (R 21 and R 22 ) are each joined in an unsubstituted carbocyclic aromatic ring containing 6 atoms; and R 5 and R 7 are each equal to methyl or ethyl.

Claim 10

Dependent Claim 83 words

The composition of claim 5 wherein R 41 and R 42 are the same and equal to methyl, (R 2 and R 5 ) and (R 3 and R 7 ) are each combined to form a six membered heterocyclic ring; R 17 , R 19 , R 20 , R 22 , R 38 , and R 39 , are the same and equal to hydrogen; and R 18 and R 21 are the same and equal to hydrogen, chloro, or methoxyl.

Claim 11

Dependent Claim 73 words

The composition of claim 4 wherein Q and T are the same and equal to S or Se, R 5 and R 7 are the same and equal to methyl or ethyl; R 17 , R 19 , R 20 , R 22 , R 38 , and R 39 are the same and equal to hydrogen; and R 18 and R 21 are the same and equal to hydrogen, chloro, or methoxyl.

Claim 12

Dependent Claim 293 words

The composition of claim 2 wherein said squarylium compound is selected from the group consisting of: ##STR19## wherein R 2 is hydrogen or substituted or unsubstituted alkyl; R 5 is (1) substituted or unsubstituted alkyl or cycloalkyl having from 1 to 6 carbon atoms or (2) substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; or R 2 and R 5 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring; Q is 0, S, Se, NR 40 , or CR 41 R 42 , where R 40 , R 41 , and R 42 are each independently alkyl of about 1 to about 6 carbon atoms or substituted or unsubstituted phenyl; R 17 , R 18 , R 19 , and R 38 are each independently hydrogen, halogen, dialkylamino, substituted or unsubstituted phenyl, substituted or unsubstituted alkyl, alkoxyl, or cycloalkyl having from 1 to 6 carbon atoms; or (R 38 and R 17 ), (R 17 and R 18 ), or (R 18 and R 19 ) are joined in a substituted or unsubstituted aromatic ring containing 5 to 7 atoms; R 23 , R 24 , R 25 , and R 26 , are each independently hydrogen or alkyl of 1 to 6 carbon atoms, substituted or unsubstituted carbocyclic or heterocyclic ring; or R 25 and R 26 are joined together to form a 5- to 7-membered heterocyclic ring; or R 23 and R 25 are joined together to form a 5- or 6-membered heterocyclic ring and independently R 24 and R 26 are joined together to form a 6-membered heterocyclic ring, and R 27 and R 28 are independently hydrogen, hydroxyl, or alkyl, alkoxyl, or cycloalkyl from 1 to 6 carbon atoms.

Claim 13

Dependent Claim 30 words

The composition of claim 11 wherein R 2 , R 17 , R 18 , R 19 , R 27 , R 28 , and R 38 are each hydrogen.

Claim 14

Dependent Claim 32 words

The composition of claim 12 wherein Q is C(CH3)2; R 5 , R 25 , and R 26 are independently methyl or ethyl; and R 23 and R 24 are each hydrogen.

Claim 15

Dependent Claim 44 words

The composition of claim 2 wherein the squarylium compound is selected from the group consisting of: ##STR20## wherein R 29 , R 30 , R 31 , and R 32 are independently hydrogen, hydroxyl, or alkyl or alkoxyl of 1 to 6 carbon atoms.

Claim 16

Dependent Claim 24 words

The composition of claim 14 wherein which R 29 and R 31 are hydrogen and R 30 and R 32 are hydrogen or hydroxyl.

Claim 17

Dependent Claim 53 words

The composition of claim 2 wherein the squarylium compound is selected from the group consisting of: ##STR21## wherein R 33 and R 34 are each independently hydrogen, halogen, substituted or unsubstituted alkyl of one to six carbon atoms, alkoxyl, or substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms.

Claim 18

Dependent Claim 28 words

The composition of claim 16 wherein R 33 and R 34 are hydrogen, alkyl, or substituted or unsubstituted aryl or heteroaryl group having from 5 to 6 atoms.

Claim 19

Dependent Claim 15 words

The composition of claim 17 wherein R 33 and R 34 are methyl or p-methoxyphenyl.

Claim 20

Dependent Claim 61 words

The composition of claim 2 wherein the squarylium compound is selected from the group consisting of: ##STR22## wherein X and Y are each independently oxygen or sulfur and R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently hydrogen or an alkyl group having from one to eight carbon atoms.

Claim 21

Dependent Claim 29 words

The composition of claim 19 wherein R 9 , R 10 , R 11 , and R 12 are each t-butyl and R 13 and R 14 are hydrogen.

Claim 22

Dependent Claim 16 words

The composition of claim 1 additionally comprising an s-triazine comprising at least one halogenated methyl group.

Claim 23

Dependent Claim 9 words

The composition of claim 21 additionally comprising a binder.

Claim 24

Dependent Claim 12 words

The composition of claim 21 wherein said halogenated methyl group comprises chloro.

Claim 25

Dependent Claim 9 words

The composition of claim 23 additionally comprising a binder.

Claim 26

Dependent Claim 147 words

The composition of claim 24 wherein said squarylium compound is selected from the group consisting of: ##STR23## wherein: R 2 is hydrogen or substituted or unsubstituted alkyl; R 5 is (1) substituted or unsubstituted alkyl or cycloalkyl having from 1 to 6 carbon atoms or (2) substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; or R 2 and R 5 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring; Q is O, S, Se, NR 40 , or CR 41 R 42 , where R 40 , R 41 , and R 42 are each independently alkyl of 1 to 6 carbon atoms or substituted or unsubstituted phenyl; R 1 5 and R 1 6 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic or heterocyclic ring; and m is 1 or 2.

Claim 27

Dependent Claim 267 words

The composition of claim 25 wherein said squarylium compound is selected from the group consisting of: ##STR24## wherein R 2 and R 3 are each independently hydrogen or substituted or unsubstituted alkyl; R 5 and R 7 are each independently (1) substituted or unsubstituted alkyl or cycloalkyl having from 1 to 6 carbon atoms or (2) substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; or R 2 and R 5 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring; and R 3 and R 7 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring; Q and T are each independently O, S, Se, NR 40 , or CR 41 R 42 , where R 40 , R 41 , and R 42 are each independently alkyl of 1 to 6 carbon atoms or substituted or unsubstituted phenyl; R 17 , R 18 , R 19 , R 20 , R 21 , R22, R 38 , and R 39 are each independently hydrogen, halogen, dialkylamino, substituted or unsubstituted phenyl, substituted or unsubstituted alkyl, alkoxyl, or cycloalkyl having from 1 to 6 carbon atoms; or (R 38 and R 17 ), (R 17 and R 18 ), or (R 18 and R 19 ) are joined in a substituted or unsubstituted aromatic ring containing 5 to 7 atoms; and, independently, (R 39 and R 20 ), (R 20 and R 21 ), or (R 21 and R 22 ) are joined in a substituted or unsubstituted aromatic ring containing 5 to 7 atoms.

Claim 28

Dependent Claim 20 words

The composition of claim 26 wherein Q and T are the same and equal to CR 41 R 42 .

Claim 29

Dependent Claim 73 words

The composition of claim 27 wherein R 41 and R 42 are the same and equal to methyl, R 5 and R 7 are the same and equal to methyl or ethyl; R 17 , R 19 , R 20 , R 22 , R 38 , and R 39 are the same and equal to hydrogen; and R 18 and R 21 are the same and equal to hydrogen, chloro, or methoxyl.

Claim 30

Dependent Claim 31 words

The composition of claim 28 wherein R 5 and R 7 are the same and equal to methyl and R 18 and R 21 are the same and equal to hydrogen.

Claim 31

Dependent Claim 74 words

The composition of claim 27 wherein R 41 and R 42 are the same and equal to methyl, R 17 , R 20 , R 38 and R 39 are the same and equal to hydrogen, (R 18 and R 19 ) and (R 21 and R 22 ) are each joined in an unsubstituted carbocyclic aromatic ring containing 6 atoms; and R 5 and R 7 are each equal to methyl or ethyl.

Claim 32

Dependent Claim 83 words

The composition of claim 27 wherein R 41 and R 42 are the same and equal to methyl, (R 2 and R 5 ) and (R 3 and R 7 ) are each combined to form a six membered heterocyclic ring; R 17 , R 19 , R 20 , R 22 , R 38 , and R 39 , are the same and equal to hydrogen; and R 18 and R 21 are the same and equal to hydrogen, chloro, or methoxyl.

Claim 33

Dependent Claim 73 words

The composition of claim 26 wherein Q and T are the same and equal to S or Se, R 5 and R 7 are the same and equal to methyl or ethyl; R 17 , R 19 , R 20 , R 22 , R 38 , and R 39 are the same and equal to hydrogen; and R 18 and R 21 are the same and equal to hydrogen, chloro, or methoxyl.

Claim 34

Dependent Claim 291 words

The composition of claim 24 wherein said squarylium compound is selected from the group consisting of: ##STR25## wherein R 2 is hydrogen or substituted or unsubstituted alkyl; R 5 is (1) substituted or unsubstituted alkyl or cycloalkyl having from 1 to 6 carbon atoms or (2) substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms; or R 2 and R 5 are joined together to form a 5- to 7-membered substituted or unsubstituted carbocyclic ring; Q is O, S, Se, NR 40 , or CR 41 R 42 where R 40 R 41 , and R 42 are each independently alkyl of about 1 to about 6 carbon atoms or substituted or unsubstituted phenyl; R 17 , R 18 , R 19 , and R 38 are each independently hydrogen, halogen, dialkylamino, substituted or unsubstituted phenyl, substituted or unsubstituted alkyl, alkoxyl, or cycloalkyl having from 1 to 6 carbon atoms; or R 38 and R 17 ), (R 17 and R 18 ), or (R 18 and R 19 ) are joined in a substituted or unsubstituted aromatic ring containing 5 to 7 atoms; R 23 , R 24 , R 25 , and R 26 , are each independently hydrogen or alkyl of 1 to 6 carbon atoms, substituted or unsubstituted carbocyclic or heterocyclic ring; or R 25 and R 26 are joined together to form a 5- to 7-membered heterocyclic ring; or R 23 and R 25 are joined together to form a 5- or 6-membered heterocyclic ring and independently R 24 and R 26 are joined together to form a 6-membered heterocyclic ring, and R 27 and R 28 are independently hydrogen, hydroxyl, or alkyl, alkoxyl, or cycloalkyl from 1 to 6 carbon atoms.

Claim 35

Dependent Claim 30 words

The composition of claim 33 wherein R 2 , R 17 , R 18 , R 19 , R 27 , R 28 , and R 38 are each hydrogen.

Claim 36

Dependent Claim 36 words

The composition of claim 34 wherein Q is C(CH 3 ) 2 ; R 5 , R 25 , and R 26 are independently methyl or ethyl; and R 23 and R 24 are each hydrogen.

Claim 37

Dependent Claim 44 words

The composition of claim 24 wherein the squarylium compound is selected from the group consisting of: ##STR26## wherein R 29 , R 30 , R 31 , and R 32 are independently hydrogen, hydroxyl, or alkyl or alkoxyl of 1 to 6 carbon atoms.

Claim 38

Dependent Claim 24 words

The composition of claim 36 wherein which R 29 and R 31 are hydrogen and R 30 and R 32 are hydrogen or hydroxyl.

Claim 39

Dependent Claim 47 words

The composition of claim 24 wherein the squarylium compound is selected from the group consisting of: ##STR27## wherein R 33 and R 34 are each independently hydrogen, halogen, substituted or unsubstituted, alkyl, alkoxyl, or substituted or unsubstituted aryl or heteroaryl group having from 5 to 10 atoms.

Claim 40

Dependent Claim 28 words

The composition of claim 38 wherein R 33 and R 34 are hydrogen, alkyl, or substituted or unsubstituted aryl or heteroaryl group having from 5 to 6 atoms.

Claim 41

Dependent Claim 15 words

The composition of claim 39 wherein R 33 and R 34 are methyl or p-methoxyphenyl.

Claim 42

Dependent Claim 61 words

The composition of claim 24 wherein the squarylium compound is selected from the group consisting of: ##STR28## wherein X and Y are each independently oxygen or sulfur and R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently hydrogen or an alkyl group having from one to eight carbon atoms.

Claim 43

Dependent Claim 29 words

The composition of claim 41 wherein R 9 , R 10 , R 11 , and R 12 are each t-butyl and R 13 and R 14 are hydrogen.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1995-09-15	1996-03-16	1996-09-15	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1999-09-15	2000-03-16	2000-09-15	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2003-09-15	2004-03-16	2004-09-15	$7700.00	Window Closed / Lapsed

Red sensitive photopolymerizable compositions

Abstract

Inventors

Bibliographic Details

Claims Analysis

References Cited (Backward Citations)

USPTO Annuity & Maintenance Windows

Assigned Categories & Tags

Assign Category Tag