Processes and compositions for photogeneration of acid

• US 5,401,607 A
• Filed: 06/29/1993
• Issued: 03/28/1995
• Est. Priority Date: 04/17/1991
• Status: Expired due to Term

• Current Assignee: Senshin Capital LLC (Intellectual Ventures LLC)
• Original Assignee: Polaroid Corporation (PLR IP Holdings LLC)
• Inventors: Telfer, Stephen J., Waterman, Kenneth C., Takiff, Larry C.
• Primary Examiner(s): Bowers, Jr., Charles L.
• Assistant Examiner(s): Letscher, Geraldine
• Application Number:
  US08/084,759
• Time in Patent Office: 637 Days
• Field of Search: 430/253, 430/270, 430/203, 430/269, 430/340, 430/346, 430/336, 430/333, 430/944, 430/945, 204/157.45, 549/331, 549/332
• US Class Current: 430/253
• CPC Class Codes: G03F 7/039 Macromolecular compounds which are photodegradable, e.g. positive electron resists G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023
• CPC Class Codes: G03F 7/346 using photosensitive materials other than non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds

Abstract

An infra-red sensitive acid-generating medium comprises a binder, an iodonium salt; and a squarylium dye capable of absorbing infra-red radiation having a wavelength within the range of about 700 to about 1200 nm, the dye having a squarylium ring the 1- and 3-positions of which are each connected, via a single sp² carbon atom, to a pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium nucleus, at least one of the sp² carbon atoms having a hydrogen atom attached thereto, and the 2-position of the squarylium ring bearing an O^-, amino or substituted amino, or sulfonamido group.

Claims

1. An acid-generating medium comprising:

a diaryl iodonium salt; and

a squarylium dye capable of absorbing infra-red radiation having a wavelength within the range of 700 to 1200 nm, the dye having a squarylium ring the 1- and 3-positions of which are each connected, via a single sp² carbon atom, to a pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moiety, at least one of the sp² carbon atoms having a hydrogen atom attached thereto, and the 2-position of the squarylium ring bearing an O^-, amino or substituted amino, or sulfonamido group.

2. A medium according to claim 1 wherein the 2-position of the squarylium ring bears an amino or substituted amino group, and at least one of the pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moieties bears at least electron-donating substituent.

3. A medium according to claim 1 wherein the infra-red dye has an oxidation potential in dichloromethane not greater than about 500 mV relative to a standard calomel electrode.

4. A medium according to claim 1 wherein the diaryl iodonium salt is an alkoxyphenyl phenyl iodonium salt.

5. A medium according to claim 4 wherein the alkoxyphenyl phenyl iodonium salt is octyloxyphenyl phenyl iodonium hexafluoroantimonate.

6. A medium according to claim 1 further comprising a binder selected from the group consisting of polystyrene, poly(α

-methylstyrene) and poly(vinyl chloride).

7. A medium according to claim 1 wherein, in the infra-red dye, one of said sp² carbon atoms does not bear a hydrogen atom.

8. A medium according to claim 1 wherein the two pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moieties are different from one another.

9. A medium according to claim 1 wherein at least one of the pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moieties is a 2-substituted or 2,6-disubstituted pyrylium or thiopyrylium group, or a 2-substituted benzpyrylium or benzthiopyrylium group, wherein the or each substituent comprises an alkyl, cycloalkyl or alkoxyphenyl group.

10. A medium according to claim 1 wherein at least one of the pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moieties is a 7-substituted benzpyrylium or benzthiopyrylium group wherein the 7-substituent is a morpholino group or a disubstituted amino group, in which each of the substituents is an alkyl or cycloalkyl group, or the two substituents on the amino group together form a polymethylene chain which, together with the nitrogen atom of the amino group, forms a heterocyclic ring, or the two substituents on the amino group are two polymethylene chains, the ends of which remote from the nitrogen atom are connected to the 6- and 8-carbon atoms of the benzpyrylium or benzthiopyrylium group.

11. A medium according to claim 1 having a first layer containing the binder, infra-red dye and diaryl iodonium salt, the first layer also comprising a depolymerizable polymer which at least partially depolymerizes in the presence of acid, the medium further comprising a layer of a porous or particulate imaging material superposed on the first layer, the layer of the imaging material having a cohesive strength greater than the adhesive strength between the imaging material and the first layer prior to depolymerization of the polymer, but less than the adhesive strength between the imaging material and the first layer after at least partial depolymerization of the polymer.

12. A medium according to claim 1 wherein the infra-red dye is of the formula:

##STR16##

13. A medium according to claim 1 further comprising a secondary acid generator capable of being thermally decomposed to form a second acid, the thermal decomposition of the secondary acid generator being catalyzed by the superacid produced by decomposition of the diaryl iodonium salt.

14. A process for generating acid, which process comprises:

providing a mixture of a diaryl iodonium salt and a squarylium dye capable of absorbing infra-red radiation having a wavelength within the range of 700 to 1200 nm, the dye having a squarylium ring the 1- and 3-positions of which are each connected, via a single sp² carbon atom, to a pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moiety, at least one of the sp² carbon atoms having a hydrogen atom attached thereto, and the 2-position of the squarylium ring bearing an O^-, amino or substituted amino, or sulfonamido group; and

irradiating the mixture with infra-red radiation having a wavelength within the range of 700 to 1200 nm, thereby causing absorption of the radiation by the squarylium dye and formation of acid in the mixture.

15. A process according to claim 14 wherein the squarylium dye has an oxidation potential in dichloromethane not greater than about 500 mV relative to a standard calomel electrode.

16. A process according to claim 14 wherein the diaryl iodonium salt is an alkoxyphenyl phenyl iodonium salt.

17. A process according to claim 14 wherein the squarylium dye and the diaryl iodonium salt are dispersed in a solid polymeric binder.

18. A process according to claim 17 wherein the binder is polystyrene, poly(α

-methylstyrene) or poly(vinyl chloride).

19. A process according to claim 14 wherein, in the squarylium dye, the two pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moleties are different.

20. A process according to claim 14 wherein, in the squarylium dye, at least one of the pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moleties is a 2-substituted or 2,6-disubstituted pyrylium or thiopyrylium group, or a 2-substituted benzpyrylium or benzthiopyrylium group, wherein the or each substituent comprises an alkyl, cycloalkyl or alkoxyphenyl group.

21. A process according to claim 14 wherein, in the squarylium dye, at least one of the pyrylium, thiopyrylium, benzpyrylium or benzthiopyrylium moleties is a 7-substituted benzpyrylium or benzthiopyrylium group wherein the 7-substituent is a morpholino group or a disubstituted amino group in which each of the substituents is an alkyl or cycloalkyl group, or the two substituents on the amino group together form a polymethylene chain which, together with the nitrogen atom of the amino group, forms a heterocyclic ring, or the two substituents on the amino group are two polymethylene chains, the ends of which remote from the nitrogen atom are connected to the 6- and 8-carbon atoms of the benzpyrylium or benzthiopyrylium group.

22. A process according to claim 14 wherein the mixture further comprises a depolymerizable polymer which at least partially depolymerizes in the presence of acid, the mixture forming the first layer of an imaging medium, this medium, this medium further comprising a layer of a porous or particulate imaging material superposed on the first layer, the layer of the imaging material having a cohesive strength greater than the adhesive strength between the imaging material and the first layer prior to depolymerization of the polymer, the process comprising imagewise exposing the imaging medium to infra-red radiation having a wavelength of 700 to 1200 nm, thereby causing absorption of the infra-red radiation by the squarylium dye, generation of acid by the diaryl iodonium salt and at least partial depolymerization of the polymer in the exposed areas of the first layer, rendering these exposed areas tacky and firmly attaching exposed portions of the imaging material layer to the first layer;

and

removing from the first layer the portions of the imaging material in the unexposed areas, but leaving the portions of the imaging material in the exposed areas adhered to the first layer, and thereby forming an image.

23. A process according to claim 14 wherein the medium further comprises a secondary acid generator capable of being thermally decomposed to form a secondary acid, the thermal decomposition of the secondary acid generator being catalyzed by the superacid produced by decomposition of the diaryl iodonium salt, and wherein, following the imagewise irradiation with infra-red radiation, the whole medium is irradiated with actinic radiation of a wavelength shorter than the wavelength of the infra-red radiation and capable of decomposing the diaryl iodonium salt, thereby causing decomposition of part of the remaining diaryl iodonium salt, with formation of free superacid in the areas exposed to the infra-red radiation.

24. A process according to claim 14 wherein the squarylium dye is of the formula:

##STR17##