EP1058864A1 - Imaging system employing encapsulated radiation sensitive composition - Google Patents

Imaging system employing encapsulated radiation sensitive composition

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Publication number
EP1058864A1
EP1058864A1 EP99908475A EP99908475A EP1058864A1 EP 1058864 A1 EP1058864 A1 EP 1058864A1 EP 99908475 A EP99908475 A EP 99908475A EP 99908475 A EP99908475 A EP 99908475A EP 1058864 A1 EP1058864 A1 EP 1058864A1
Authority
EP
European Patent Office
Prior art keywords
microcapsules
photosensitive material
sensitive
complex
anion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99908475A
Other languages
German (de)
French (fr)
Inventor
Alex Polycarpov
Joseph C. Camillus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Cycolor Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cycolor Inc filed Critical Cycolor Inc
Publication of EP1058864A1 publication Critical patent/EP1058864A1/en
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/002—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using materials containing microcapsules; Preparing or processing such materials, e.g. by pressure; Devices or apparatus specially designed therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images

Definitions

  • imaging system employs a layer of photosensitive microcapsules.
  • the microcapsules are prepared by microencapsulating a free radical polymerizable composition which contains an electron donating color precursor.
  • the image system assumes two forms.
  • the imaging system is a transfer system in which a support carrying a layer of photosensitive microcapsules is image-wise exposed to radiation and assembled with a developer sheet, e.g., a sheet containing a layer of a Lewis acid such as a phenolic resin.
  • the imaging system is a self-contained imaging system in which the photosensitive microcapsules and the Lewis acid are carried on the surface of a common substrate in one layer or in juxtaposed layers.
  • a layer containing photosensitive microcapsules and a developer material is interposed between two plastic films, at least one of which is transparent. Using a combination of an adhesive and a subbing layer, the films are permanently sealed to provide a film unit. This construction is advantageous because it prevents the chemical reactants in the imaging system from coming into contact with the user.
  • the imaging system is preferably a full color imaging system in which three different sets of microcapsules are used in combination and each set of microcapsules is sensitive to a distinct wavelength band.
  • This full color system is described in U.S. Patent 4,842,976.
  • three sets of microcapsules respectively containing cyan, magenta and yellow color precursors are respectively sensitive to red, green and blue light are employed.
  • these microcapsules are sensitized using a so-called "dye-borate photoinitiator" of the type described in U.S. Patent 4,772,530 to Gottschalk.
  • photoinitiators in one embodiment, are complexes of cationic cyanine dyes and a boranyl anion such as a triphenylbutylboranyl anion.
  • a boranyl anion such as a triphenylbutylboranyl anion.
  • printers can be designed which employ radiation sources which emit at wavelengths outside the visible spectrum, for example, in the infrared region. This presents an opportunity to minimize the problems associated with cross-talk since it is no longer necessary to restrict the sensitivity range of a photosensitive material to the visible region, the sensitivity of the imaging system can be extended into the infrared region at one end of the spectrum and optionally the ultraviolet region at the other end.
  • the foregoing imaging system and, more particularly, the imaging system described in U.S. Patent 4,772,530 is modified to include one or more infrared photosensitive compositions and, more particularly, to include one or more photosensitive compositions in which the photoinitiator is a complex between an infrared-sensitive dye and a boranyl anion of the type mentioned above.
  • one embodiment of the invention resides in an imaging system comprising a support having a layer of at least one set of photosensitive microcapsules on the surface thereof, said microcapsules being sensitive to distinct band of radiation and containing a complex of an infrared sensitive cationic dye and a boranyl anion.
  • the imaging system includes cyan forming, magenta forming and yellow forming capsules and at least one set of capsules includes an infrared sensitive dye borate compound as a photoinitiator.
  • at least one other set includes a visible light sensitive dye borate compound or an ultraviolet initiator.
  • all three sets of microcapsules contain a photohardenable composition containing a complex of a cationic infrared sensitive dye and a boranyl anion.
  • infrared-sensitive photoinitiators which can be employed in the imaging system of the present invention are described in Japanese Published Applications 3- 221506; 4-261405; 8-100011; 8-100012; and 8-34808, all of which are incorporated herein by reference for a description of the cationic dyes and methods for obtaining the photoinitiators.
  • a table of the infrared sensitive cationic dyes described in the aforementioned patents is provided in the following Table 1 where "Ph" indicates a phenyl group:
  • the infrared dyes in Table 1 are complexed with a borate anion.
  • a borate anion Any of the borate anions described in U.S. Patent 4,772,530 can be used in this invention.
  • the preferred boranyl anion is a triphenyl n-butylboranyl anion.
  • the anions can be represented by the general formula (I):
  • R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic groups.
  • triphenylalkylborate and trianisylalkylborate anions such as triphenylbutylborate and trianisylbutylborate anions because they readily dissociate to triphenylborane or trianisylborane and a butyl radical.
  • tetrabutylborate anion does not work well presumably because the tefrabutylborate radical is not stable and it readily accepts an electron back from the dye in a back electron transfer and does not dissociate efficiently.
  • tetraphenylborate anion is very poor because the phenyl radical is not easily formed.
  • R 1 , R 2 , R 3 , and R 4 is an alkyl group.
  • R 1 , R 2 , R 3 , and R 4 is an alkyl group.
  • R 1 , R 2 , R 3 , and R 4 can contain up to 20 carbon atoms, and they typically contain 1 to 7 carbon atoms. More preferably R'-R 4 are a combination of alkyl group(s) and aryl group(s) or aralkyl group(s) and still more preferably a combination of three aryl groups and one alkyl group.
  • alkyl groups represented by R'-R 4 are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, stearyl, etc. and can be straight or branched chain and possibly cyclic.
  • the alkyl groups may be substituted, for example, by one or more halogen, cyano, acyloxy, acyl, aryl, alkoxy or hydroxy groups.
  • aryl groups represented by R0R 4 include phenyl, naphthyl and substituted aryl groups such as anisyl.
  • Alkaryl groups include methylphenyl, dimethylphenyl, etc.
  • Representative examples of aralkyl groups represented by groups include benzyl.
  • Representative alicyclic groups include cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of an alkynyl group are propynyl and ethynyl, and examples of alkenyl groups include a vinyl group.
  • an infrared sensitive dye borate in at least one set of the microcapsules enable the sensitivities of the microcapsules to be spaced apart to minimize overlap in their sensitivity curves and thereby minimize crosstalk.
  • Infrared sensitive borates can be used in any or all of the cyan, magenta or yellow forming microcapsules.
  • an imaging system can be designed in which the microcapsules are sensitive at 750, 850 and 1050 nm.
  • the red sensitive capsules described in U.S. Patent 4,772,530 (Gottschalk) are replaced with infrared sensitive microcapsules prepared using one of the dyes in the appendix such as the dye #5 in Table 1.
  • an imaging system can be designed in which the microcapsules are sensitive at 800, 900 and 1100 nm.
  • the cyan, magenta and yellow forming microcapsules are sensitive at 450, 550, 650 nm respectively.
  • any of 450, 550, and 650 sensitizers is replaced with an infrared dye.
  • the magenta 550 initiator is replaced with an infrared dye to achieve the most separation in the absorptions.
  • a 450, 840, 650 nm system might be used.
  • the infrared sensitive compositions can be modified to include an autoxidizer such as N,N-dimethylaniline as described in U.S. Patent 4,772,530 which is incorporated herein by reference.
  • an autoxidizer such as N,N-dimethylaniline as described in U.S. Patent 4,772,530 which is incorporated herein by reference.
  • the ultraviolet initiator can be selected from among those that are known in the art. Some examples are provided in U.S. Patent 4,399,209.
  • the infrared sensitive dye is normally used in an amount up to 1 % by weight based on the weight of the photopolymenzable species and more typically in an amount of about 0.2 to 0.5% by weight. However, those skilled in the art will recognize that the amount is easily adjusted to achieve the desired sensitivity and photographic response in the photosensitive material.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

A photosensitive material comprising a support having a layer of microcapsules on one surface thereof, the microcapsules having an image-forming agent associated therewith and containing an internal phase including a photohardenable composition, the composition comprising a free radical addition polymerizable or crosslinkable compound and complex of an infrared sensitive cationic dye and a boranyl anion being capable of absorbing infrared radiation and producing free radicals which initiate free radical polymerization or crosslinking of the polymerizable or crosslinkable compound.

Description

IMAGING SYSTEM EMPLOYING ENCAPSULATED RADIATION SENSITIVE COMPOSITION
CROSS-REFERENCE TO RELATED APPLICATIONS
The present invention claims priority under 35 U.S.C. §119 from Provisional Patent Application Serial No. 60/075,892, filed February 25, 1998.
BACKGROUND OF THE INVENTION
This application is directed to an improvement in the imaging system which is described in U.S. Patents 4,399,209, 4,440,846 and 4,772,530 to Cycolor, Inc. These imaging systems employ a layer of photosensitive microcapsules. The microcapsules are prepared by microencapsulating a free radical polymerizable composition which contains an electron donating color precursor. Typically the image system assumes two forms. In one, the imaging system is a transfer system in which a support carrying a layer of photosensitive microcapsules is image-wise exposed to radiation and assembled with a developer sheet, e.g., a sheet containing a layer of a Lewis acid such as a phenolic resin. The assembly is subjected to pressure to rupture the microcapsules and the microcapsules image- wise leak their contents to the developer sheet where the color precursor is colored. In another embodiment, the imaging system is a self-contained imaging system in which the photosensitive microcapsules and the Lewis acid are carried on the surface of a common substrate in one layer or in juxtaposed layers. In a further embodiment of the invention, as described in U.S. Application Serial No. 08/570,658 and published International Application WO 95/34845, a layer containing photosensitive microcapsules and a developer material is interposed between two plastic films, at least one of which is transparent. Using a combination of an adhesive and a subbing layer, the films are permanently sealed to provide a film unit. This construction is advantageous because it prevents the chemical reactants in the imaging system from coming into contact with the user.
The imaging system is preferably a full color imaging system in which three different sets of microcapsules are used in combination and each set of microcapsules is sensitive to a distinct wavelength band. This full color system is described in U.S. Patent 4,842,976. In accordance with one commercial manifestation of the imaging system, three sets of microcapsules respectively containing cyan, magenta and yellow color precursors are respectively sensitive to red, green and blue light are employed. In a further embodiment, these microcapsules are sensitized using a so-called "dye-borate photoinitiator" of the type described in U.S. Patent 4,772,530 to Gottschalk. These photoinitiators, in one embodiment, are complexes of cationic cyanine dyes and a boranyl anion such as a triphenylbutylboranyl anion. For making photocopies and other applications employing visible light sources, imaging systems employing red-sensitive, blue-sensitive and green-sensitive microcapsules are desirable but one of the difficulties that is encountered in designing an imaging system with red, green and blue sensitivity is crosstalk. That is, the absorption spectra of the red and/or green and/or blue photoinitiators may overlap. In this case, it is important that in exposing the microcapsule to limit the amount of light which occurs in an overlapping region. Otherwise, the color quality of the reproduction will not be good. The art discloses a number of approaches that can be taken to mitigate this problem. However, with the proliferation of digital imaging systems, there are a host of applications in which red, green and blue sensitivity is not required. In particular printers can be designed which employ radiation sources which emit at wavelengths outside the visible spectrum, for example, in the infrared region. This presents an opportunity to minimize the problems associated with cross-talk since it is no longer necessary to restrict the sensitivity range of a photosensitive material to the visible region, the sensitivity of the imaging system can be extended into the infrared region at one end of the spectrum and optionally the ultraviolet region at the other end.
-2- SUMMARY OF THE INVENTION
In accordance with the present invention, the foregoing imaging system and, more particularly, the imaging system described in U.S. Patent 4,772,530, is modified to include one or more infrared photosensitive compositions and, more particularly, to include one or more photosensitive compositions in which the photoinitiator is a complex between an infrared-sensitive dye and a boranyl anion of the type mentioned above.
Accordingly, one embodiment of the invention resides in an imaging system comprising a support having a layer of at least one set of photosensitive microcapsules on the surface thereof, said microcapsules being sensitive to distinct band of radiation and containing a complex of an infrared sensitive cationic dye and a boranyl anion.
In another embodiment, the imaging system includes cyan forming, magenta forming and yellow forming capsules and at least one set of capsules includes an infrared sensitive dye borate compound as a photoinitiator. Optionally at least one other set includes a visible light sensitive dye borate compound or an ultraviolet initiator.
In still another embodiment, all three sets of microcapsules contain a photohardenable composition containing a complex of a cationic infrared sensitive dye and a boranyl anion.
DETAILED DESCRIPTION OF THE INVENTION
Examples of infrared-sensitive photoinitiators which can be employed in the imaging system of the present invention are described in Japanese Published Applications 3- 221506; 4-261405; 8-100011; 8-100012; and 8-34808, all of which are incorporated herein by reference for a description of the cationic dyes and methods for obtaining the photoinitiators. A table of the infrared sensitive cationic dyes described in the aforementioned patents is provided in the following Table 1 where "Ph" indicates a phenyl group:
-3- Table 1
Dye λmax (TMPT)
o> CH — (CH=CH>3- 820nm
C2 HS C 2 H5
CC2 H5 ) 2N K (C, H 5« ϊ 2 λ. C. =. CH -CH = CH-c 830nm
X)
(C Ht ) 2N ^ (C2 H5 K C=CH-CH=CH-C 822nm
|(C, H, ) 2N X N (C2 H5 ) 2
Or CH — 6CH-CH
" x 768nm
C 2 H5 C2 H5
CH, CH,
CH, CH, (CH = CH*
;N 748nm
I
CH CH
CHg C 785nm
CH — (CH = CH>
-4- Dye λmax (TMPT)
CH, CH,
CH CH, N' = CH ■-CH-Ω- CH-CH- 787nm
C2 H4 OCH3 C2 H4 OCH3
CH, CH,
CH3 CH. CH CH-CH- 813nm N' •CH- N
C7H: 15 -9- C7H15
-5- Dye" λmax (CHC/3)
!^ N^ φ-CH^ XN ) 428nm
CH, CH,
C^CH-CH-CH- ϊΦ ! 450nm
C Ho C Hr CHo CH,
l^ζ^ - C H = C H - C H ^^ j) I© ,
CH2— ^CH2^-CH3 CH2— ^CH2 CH3 492nm
CH, CH,
CH, CH,
?s — •CH-CH-CH- NJ Jl 550πm
I
C H C H, CH Hg
z N -CH=CH-CH
CH2-^CH2VCH3 CH2"~ *CH2 "CH3 568nm
ζ^ — 6CH=CH -CH:^ J
I Θ I
590nm
CH, CH, CHo CH,
CH, CH, r CH C Ho tCH = CH^-CH> JO 640nm
CHo C H, C H C H
-6- No. Dye
15 ^*s - 7. -^^ 814nm
1
CH3 1
CH3
The infrared dyes in Table 1 are complexed with a borate anion. Any of the borate anions described in U.S. Patent 4,772,530 can be used in this invention. The preferred boranyl anion is a triphenyl n-butylboranyl anion. The anions can be represented by the general formula (I):
\ /
where R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic groups.
For example particularly preferred anions are triphenylalkylborate and trianisylalkylborate anions such as triphenylbutylborate and trianisylbutylborate anions because they readily dissociate to triphenylborane or trianisylborane and a butyl radical. On the other hand tetrabutylborate anion does not work well presumably because the tefrabutylborate radical is not stable and it readily accepts an electron back from the dye in a back electron transfer and does not dissociate efficiently. Likewise, tetraphenylborate anion is very poor because the phenyl radical is not easily formed. Preferably, at least one but not more than three of R1, R2, R3, and R4 is an alkyl group. Each of R1, R2, R3, and R4 is an alkyl group. Each of R1, R2, R3, and R4 can contain up to 20 carbon atoms, and they typically contain 1 to 7 carbon atoms. More preferably R'-R4 are a combination of alkyl group(s) and aryl group(s) or aralkyl group(s) and still more preferably a combination of three aryl groups and one alkyl group.
Representative examples of alkyl groups represented by R'-R4 are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, stearyl, etc. and can be straight or branched chain and possibly cyclic. The alkyl groups may be substituted, for example, by one or more halogen, cyano, acyloxy, acyl, aryl, alkoxy or hydroxy groups.
Representative examples of aryl groups represented by R0R4 include phenyl, naphthyl and substituted aryl groups such as anisyl. Alkaryl groups include methylphenyl, dimethylphenyl, etc. Representative examples of aralkyl groups represented by groups include benzyl. Representative alicyclic groups include cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of an alkynyl group are propynyl and ethynyl, and examples of alkenyl groups include a vinyl group.
Other infrared sensitive complexes useful as photoinitiators in the invention described in Japanese Application 4-261405 are shown in Table 2:
-8- Table 2
(A)
Ar R phenyl n-butyl
Ar A anisyl n-hexyl
(CH3CH2 ) 2N~ _/~ N 2 + I B Ni Ar-B-R
I phenyl n-octyl C ■ Ar
phenyl n-butyl
Ar A (CH3CH2) 2N- V-N 2 + I anisyl n-hexyl B Cu Ar-B-R C I phenyl n-octyl Ar
phenyl n-butyl
Ar A (CH CH + I anisyl n-hexyl B )2Ni 2
:NI Ar-B-R C phenyl n-octyl Ar
(B)
Ar R
Ar phenyl n-butyl A (CH3CH2) 2N I B Ar-B-R anisly n-hexyl C I Ar phenyl n-octyl
P
(CH3CH,CH2) 2N ~ ~N I Ph-B-Bu 1 Ph
> 2
Ph
(CH3CH2CH2) ,N- _ -N I Ph-B-Bu
I Ph
-9- (C)
Ar R
KCC2H4
\ Ph
2 +
/ Nl Ph-B-Bu
NCC2H4 Ph
CH CH
Ph
N-/ -N 2 + t
:Cu Ph-B-Bu
NCC-H, I Ph
(D)
Ar R
Ar phenyl n-butyl A (CH 00CC2H4) 2t N SHB IN i Ai -B-R anisyl n-hexyl Cϋ I C Ar phenyl n-octyl
phenyl n-butyl
Ar A (CH3OOCC2H4) 2NF — f_ — N =/ = a 2 + I B :cu Ar-B-R anisyl n-hexyl C ^ Cfi f~ — - I Ar phenyl n-octyl
phenyl n-butyl A Λr
( E3OC2fl4J 2N - ~\-N 2 + I B Ar-B-R anisyl n-hexyl C CH3CONH I Ar phenyl n-octyl
Ph
(H0C2H4) 2 N- ~ - N 2- I Ph-B-Bu
CH30 I , Ph'
-10- (E)
Ar R
CH3
Ar phenyl n-butyl
\ A N 2 + I B / :N : Ar-B-R anisyl n-hexyl
(CH^OOCC 2H4 2 C "&• I Ar phenyl n-octyl
C4H9
\ Ph
M N 2 + I
/ :NI Ph-B-Bu Ph
CH.
Ph
(CH3CH2) N 2 + I
:N Ϊ Ph-B-Bu I Ph
CH.
Ph
(CH3CE2 2- I
:cu Ph-B-Bu I Ph
(F)
Ar R
Ph
(CH3CH2) 2N Ph-B-Bu Ph
Ar phenyl n-butyl
(CH^CH, ) oN I Ar-B-R anisyl n-hexyl
I Ar phenyl n-octyl
-11- Ar R
Bu
37 (CH3CH2) 2N I Bu-B-S IPhMβ,
I
Bu
Ph
38 fCH3OOCC H4) 2N I Bu-B-S i PhMe3 I Ph
Using an infrared sensitive dye borate in at least one set of the microcapsules enable the sensitivities of the microcapsules to be spaced apart to minimize overlap in their sensitivity curves and thereby minimize crosstalk. Infrared sensitive borates can be used in any or all of the cyan, magenta or yellow forming microcapsules. In one example, an imaging system can be designed in which the microcapsules are sensitive at 750, 850 and 1050 nm. In another embodiment, the red sensitive capsules described in U.S. Patent 4,772,530 (Gottschalk) are replaced with infrared sensitive microcapsules prepared using one of the dyes in the appendix such as the dye #5 in Table 1. In another embodiment an imaging system can be designed in which the microcapsules are sensitive at 800, 900 and 1100 nm. In conventional systems, the cyan, magenta and yellow forming microcapsules are sensitive at 450, 550, 650 nm respectively. In other embodiments of the invention, any of 450, 550, and 650 sensitizers is replaced with an infrared dye. Preferably the magenta 550 initiator is replaced with an infrared dye to achieve the most separation in the absorptions. For example, a 450, 840, 650 nm system might be used.
The infrared sensitive compositions can be modified to include an autoxidizer such as N,N-dimethylaniline as described in U.S. Patent 4,772,530 which is incorporated herein by reference. Likewise, microcapsules for encapsulating the photohardenable composition, cyan, magenta and yellow color precursors, developer materials, photohardenable compositions including photopolymerizable acrylate
-12- compositions are described in detail in U.S. Patent 4,772,530. If it is desired to use an ultraviolet initiator in one or more sets of microcapsules, the ultraviolet initiator can be selected from among those that are known in the art. Some examples are provided in U.S. Patent 4,399,209.
The infrared sensitive dye is normally used in an amount up to 1 % by weight based on the weight of the photopolymenzable species and more typically in an amount of about 0.2 to 0.5% by weight. However, those skilled in the art will recognize that the amount is easily adjusted to achieve the desired sensitivity and photographic response in the photosensitive material.
Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.
What is claimed is:
-13-

Claims

1. A photosensitive material comprising a support having a layer of microcapsules on one surface thereof, said microcapsules having an image-forming agent associated therewith and containing an internal phase including a photohardenable composition, said composition comprising a free radical addition polymerizable or crosslinkable compound and complex of an infrared sensitive cationic dye and a boranyl anion being capable of absorbing infrared radiation and producing free radicals which initiate free radical polymerization or crosslinking of said polymerizable or crosslinkable compound.
2. The photosensitive material of claim 1 wherein said boranyl anion is represented by the formula I:
Rl R4
\ /
B- y \.
where R1, R2, R3, and R4 are independently selected from the group consisting of alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic groups.
3. The photosensitive material of claim 2 wherein said material is useful in forming full color images and said microcapsules include a first set of microcapsules having a cyan image-forming agent associated therewith, a second set of microcapsules having a magenta image-forming agent associated therewith and a third set of microcapsules having a yellow image-forming agent associated therewith, at least one of said first, second and third sets of microcapsules containing said photohardenable composition contain said complex.
4. The photosensitive material of claim 3 wherein said material is useful in forming images by a process which comprises the steps of image-wise exposing said microcapsules to three distinct wavelengths of actinic radiation which respectively harden said first, second and third sets of microcapsules and subjecting said microcapsules to a uniform rupturing force.
-14-
5. The photosensitive material of claim 4 wherein at least one of said wavelengths is greater than 800 nm.
6. The photosensitive material of claim 5 wherein at least one of said sets of microcapsules, other than said set containing said complex, contains a visible light sensitive complex of a cationic dye and a boranyl anion.
7. The photosensitive material of claim 5 wherein at least one of said sets of microcapsules, other than said set containing said complex, contains an ultraviolet sensitive photoinitiator.
8. The photosensitive material of claim 1 wherein the complex is a complex of a dye selected from the dyes in Table 1 or Table 2.
9. The photosensitive material of claim 3 wherein one set of microcapsules is sensitive at about 800 nm, another set is sensitive at about 900 nm and a third set is sensitive at about 1100 nm.
-15-
EP99908475A 1998-02-25 1999-02-25 Imaging system employing encapsulated radiation sensitive composition Withdrawn EP1058864A1 (en)

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US7589298P 1998-02-25 1998-02-25
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US8465973B2 (en) 2004-09-14 2013-06-18 Estee Lauder Coordination Center N.V. Topical compositions containing phosphorylated polyphenols

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US7172991B2 (en) 2001-10-11 2007-02-06 Hewlett-Packard Development Company, L.P. Integrated CD/DVD recording and labeling

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DE3677527D1 (en) * 1985-11-20 1991-03-21 Mead Corp IONIC COLORS AS PHOTOSENSITIVE MATERIALS CONTAINING INITIATORS.
KR910001448A (en) * 1989-06-30 1991-01-30 로레인 제이. 프란시스 Cationicly initiated compositions containing ionic dye reactive counterionic complexes and onium salts as photoinitiators and photosensitive materials using the same
EP0438123B1 (en) * 1990-01-16 1995-09-13 Showa Denko Kabushiki Kaisha Near infrared polymerization initiator
JP2956245B2 (en) * 1991-02-15 1999-10-04 昭和電工株式会社 Photopolymerization initiator

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8465973B2 (en) 2004-09-14 2013-06-18 Estee Lauder Coordination Center N.V. Topical compositions containing phosphorylated polyphenols

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CA2319603A1 (en) 1999-09-02

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