CA1166062A - Fixing of tetra (hydrocarbyl) borate salt imaging systems - Google Patents
Fixing of tetra (hydrocarbyl) borate salt imaging systemsInfo
- Publication number
- CA1166062A CA1166062A CA000375876A CA375876A CA1166062A CA 1166062 A CA1166062 A CA 1166062A CA 000375876 A CA000375876 A CA 000375876A CA 375876 A CA375876 A CA 375876A CA 1166062 A CA1166062 A CA 1166062A
- Authority
- CA
- Canada
- Prior art keywords
- groups
- borate
- tetra
- hydrocarbyl
- alkyl
- 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.)
- Expired
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
- G03C1/735—Organo-metallic compounds
Abstract
FIXING OF TETRA (HYDROCARBYL) BORATE
SALT IMAGING SYSTEMS
Abstract It is highly desirable to have light sensitive imaging systems which do not use expensive silver materials in their construction, yet still have some of the properties of silver imaging systems such as their ability to be fixed.
Light sensitive systems using tetra(hydrocarbyl) borates are easily constructed and do not require expen-sive materials therein. It has been found that the borates may be fixed by converting the tetra(hydrocarbyl) borate to a compound which does not have four carbon-to-boron bonds.
SALT IMAGING SYSTEMS
Abstract It is highly desirable to have light sensitive imaging systems which do not use expensive silver materials in their construction, yet still have some of the properties of silver imaging systems such as their ability to be fixed.
Light sensitive systems using tetra(hydrocarbyl) borates are easily constructed and do not require expen-sive materials therein. It has been found that the borates may be fixed by converting the tetra(hydrocarbyl) borate to a compound which does not have four carbon-to-boron bonds.
Description
FIXING OF TETRAt HYDROCARBYL ) BORATE
SALT IMAGING SYSTEMS
Field of the I~vention This invention relates to imaging processes and S in particular to dye bleaching image forming systems. A
light sensitive system comprising a dye and a tetra(hydrocarbyl)borate is shown to be capable of being rendered light-insensitive, i.e., fixed, after development.
Bac~round of the Invention There exists a vast array of imaging systems having a multitude of various constructions and composi-tions. Amongst the more widely used systems are silver halide light sensitive systems (including black and white and color photography, dry silver photothermography, instant photography, and diffusion transfer systems, amongst others), photopolymeric sys~ems (including planographic and relief printing plates, photoresist - etching systems, and imaging transfer systems), diazonium color coupling systems, and others. Each system has its own properties attributable to the phenomenon which Eorms the basis of the imaging technology. For example, silver halide imaging systems are noted both for ampli~ication (i.e., image densities which can be increased by further 25 development without additional imagewise exposure) due to the catalytic action of silver towards the reduction of silver ion and for the ~act that light sensitivity may be stopped after development by washing away the light sensitive silver halide salt (i.e., fixing)~ Photo-30 polymeric systems are noted for image stability and easeof application of the imaging layer. Diazonium color coupling systems have high image resolution and are easy to coat onto supporting substrates.
.
One other type of imaging system which has received some attention in recent years uses a salt com-prising an aromatic tetra(hydrocarbyll borate anion as a dye-bleaching or solubility-altering photosensitive compound. U~S. Patent No. 3,567,453 discloses the use of such borate salts (having at least one aryl substituent on the borate) in photoresist and lithographic compositions.
U.S. Patent ~o 3,754,921 discloses an imaging system comprising a leucophthalocyanine and "phenylboronate".
U.S. Paten~ No. 3,716,366 even indicates that image stabilization might be achieved by reaction or dissolution and removal of one of the components (column 5, lines 1-8). British Patents 1,370,058; 1,370,059; 1,370,060;
and 1,386,269 also disclose dye bleaching processes using aromatic borates as light sensitive agents.
U.S. Patent No. 3,716,366 suggests that desensi-tization may be effected by reactions with one of the components to form stable colorless products, and specifically suggests selectively dissolving out one of the components. No specific reagents or reaction mechanisms are suggested for the desensiti~ation proces~, however.
Summary of the Invention It has been found that light sensltive imaging systems having a tetra~hydrocarbyl) borate as a light sensitive component thereoE may be rendered light insensitive, particularly after imaging has been effected, by converting the borate to a product which does not have four carbon-to-boron bonds. The most useful borate containing light sensitive systems comprise a borate and a dye in a binder. Cationic dyes are particularly useful.
11~6~
Detailed Descriptlon o the In~ention Borates are variously reEerred to in the art as borates, boronates, boronides and by other chemical terms, In the practice of the present invention borates are strictly defined as tetra(hydrocarbyl)borates, that ls, a compound having four carbon-to-boron bonds. These compounds may be represented by the formula:
R4 ~1 > B ~ X~
` lO R3 \ R2 wherein Rl, R2, R3, and R4 are independently any groups bonded to the boron from a carbon atom, and X~ is any cation except H~ and boron carbon bond cleaving cations.
The groups Rl, R2, R3, and R4 may be independently selected from such groups as alkyl, aryl, aIkaryl, allyl, arylalkyl, alkenyl, alkynyl, cyano, heterocyclic rings, alkyl-heterocyclic rings, etc. Any group bonded to the boron from a carbon atom is useEul. When these substituents are referred to as groups, i.e., alkyl group versus alkyl, that nomenclature specifically is defined as allowing for substitution on the alkyl moiety ~e.g., ether or thioether linkages in the alkyl chain, halogen, cyano, vinyl, acyloxy, or hydroxy substitution, etc.), remember-ing that the group must be bonded to the boron ~rom acarbon atom. Thus, alkoxy and phenoxy would not be included. Cycloaliphatic groups are included in the definitions, as are heteroayclic groups bonded to the boron from a ring carbon atom or through an alkyl linkage (i.e., alkyl-heterocyclic). It is preferred that the R
groups be selected from aryl (e.g., phenyl or naphthyl groups3, alkyl (e.g., methyl, octyl, stearyl), alkenyl, alkynyl, allyl, and alkaryl (e g., benzyl) groups~
Preferably these groups contain no more than 20 carbon atoms. More preferably they contain no more than 12 carbon atoms and most preferably no more than 8 c~rbon atoms. Cyano is the least preferred aliphatic group.
The more preferred borates are those having at least three aliphatic groups bonded to the boron, and the most pre~erred borates have four aliphatic groups bonded to the boron.
Any cation may be used in association with the borate except for cations which break at least one carbon to boron bond on the borate, e.g., H+. As a standard test, one could limit the cations to those which do not break at least one carbon to boron bond of tetraphenyl-borate. This can be readily determined by standard analytical techniques such as gas chromatography, infrared or mass spectrometry, nuclear magnetic reasonance, etc.
It is highly preerred that the cations, if they are metal cations, be less readily reducible than ferric ions.
Readily reducible metal ions are undeslrable as they tend to fix or react with the borate. Organic cations are preferred. The nature of the cation has not been found to be critical in the practice of the present invention. The most significant contribution of the cation may be its effects upon solubility in different solvents or binders.
The cations may range from simple elemental cations such as alkali metal cations (e.g., Li+, Na~. and K~) to complex cationic dyes and quaternary ammonium cations, e.g., such as represented by the formula:
R8 - N~ - R6 wherein R5, R6, R7, and R8 are independently selected from aliphatic (e.g., alkyl and particularly alkyl of 1 to 12 or preferably 1 to 4 carbon atoms), aryl (e.g., phenyl and naphthyl groups), and aralkyl (e.g., benzyl groups). For example, tetramethyl, tetraethyl, tetrapropyl, tetrabutyl and triethyl-monomethyl ammonium are particularly useful. Ca~ions such as phenyltrimethylammonium and benzyltriethyl-:~66~
ammonium are also quite satisfactory as are phosphoniums and sulfoniums. Quaternary cations in more complex forms such as quaternary dyes and quaternized groups in polymer chains are useful. The polymers, for example, could contain repeating groups such as:
U
CH3/ c~3 b. ~CH2 - CHt [~
N (CH3)3 c. ~CH2 - CHtm ~CH2 - CH~
N ~ N -(CH3) d. tl+ ~ CH2CH2CH2 ~ Nlt+n and e. ~C~2 - CH~
O ~ \~I-CH2 - CH2 - CH2 ~ N(C~3)3 H
wherein m and n represent positive whole integers.
With the proper selection of the quaternary ammonium cations, such polymeric materials could also serve as a binder for the system.
The dyes, for example, may be of any color and any chemical class. These dyes, of course, should not contain groups which would fix or densensitize the borate salts (e.g., carboxylic and groups, sulfonic acid groups, metal ions more readily or as readily reducible than ferric ion). ~ny dye may be used in the practice of the present invention. Specific classes of dyes useful in the practice of the present invention include me~hines, triarylmethanes, cyanines, ketomethylenes, styryls, xanthines, azines, carbocyanines, butadienyls, azomethines, etc. The following are specific examples of dyes used in the practice of the present invention:
~ CH3 CH3 ~
(magenta dye N ~ ~ cation, CH3 CH3 Indolenine Red) ~ ~ CH ~ cation) 2S ~ C ~ N /Cc~3 ~ ~ N\ (cyan dye cation) When cationic dyes have been used, a slight excess of borate anion is desired to provide complete bleaching~
'6~2 `
.
The cationic dyes may have anions other than borates, such as the ionic dyes of the formula:
((C~3C~12~C~ (C~2c~3~2 wherein X is any anion including Cl , I , Br perfluoro(4-ethylperfluorocyclohexane)sulfonate, sulfate, methyl sulfate, methanesulfonate, etc.
R9 and R10 are independently H, alkyl or alkoxy (preferably 1 to 12 carbon atoms and most preferably 1 to 4 carbon atoms), Cl, Br, and I, and Rll is H or alkyl, preferably of 1 to 12 and most preferably 1 to 4 carbon atoms.
Any cationic dye is useful in the practice cf the present lS invention, and their listing is merely cumulative.
Imaging in the light sensitive systems comprising tetrahydrocarbyl borate! dye and binder is effected by irradiation. The radiation which is absorbed by the dye-borate system causes the dye to bleach. A
positive image is thus produced~ The use o~ cationic dyes is believed to spectrally sensitize the borates to radiation absorbed by the dyes associated with the borate.
These are not sensitizing dyes as used in photographic imaging systems tusually in ratios of 1/500 or 1/10,000 of dye to light sensitive agents). These dyes are used in proportions of at least 1/10 to about 1/1 in ratio to the borates. Because the dye-borate system is spectrally sensitive, a multiplicity of colored dyes may be used (e.g., cyan, magenta, and yellow) in the sa~e or different layers.
The binders useful in the present invention must be transparent or at least translucent. According to some practices of the present invention, the layers need not be penetrable by solvents or gases.~ Binders such as natural resins (e.g., gelatin, gum arabic, etc.), synthetic resins ~e.g., polyacrylates, polyvinyl acetals, cellulose esters, polyamides, polycarbonates, polyolefins, polyurethanes, polyepoxides, polyoxyalkylenes, polyvinylhalides, polysi-loxanesl polyvinylacetate, polyvinyl alcohol, etc.), and S other media may be used. The binders may be thermoplastic or highly crosslinked.
The desensitization or fixing of the light sensi-tive tetrahydrocarbyl borates is effected by disrupting a~
least one of the carbon-to-boron bonds so that there are no longer four carbon-to-boron bonds in the compound. The compound may still have four bonds to the boron, but if at least one is no longer a carbon-to-boron bond, the result-ing dye-borate system will not be usefully light sensitive and the resulting image will be stable. The conversion of the borates having four carbon-to-boron bonds to compounds having fewer than four carbon-to-boron bonds can be effected in a variety of fashions. Introducing an acid to reactive association with the tetrahydrocarbyl borate will effect such a conversion. This has been done for example, by subjecting the sheet to hydrochloric acid vapor, coating the sheet lightly with acetic acid, placing an acid containing polymeric sheet in temporary or permanent association with the imaging sheet and heating the composite, or including an acid-releasing light sensitive material in the sheet and irradiating the material (where it is sensitive to a different portion of the spectrum than the dye-borate system). The useful acids include for example, carboxylic acids (e.g., acetic acid, stearic acid, etc.), inorganic acids (e.g., nitric acid, sulfuric acid, hydrobromic acid, hydrochloric acid, sulfamic acid,), and organic acids other than carboxylic acids (e.g., aliphatic sulfonic and sulfonylic acids, fluorinated or perfluorinated carboxylic acids, etc.).
Other materials which may be applied to the sheet in similar fashions include aldehydes (particularly by vapor treatment), peroxides, iodine, readily reducible metal ions, and quinones. These materials need only be g introduced into reactive association ~ith the tetra(hydrocarbyl) borate to ef~ect fixing. Reactive association is defined as such physical proximity between materials as to enable a chemical reaction to take place between themO
The acids and acidic substances useful in the present invention as fixers generally have a PKa of less than 9, preferably a PKa f less than 7, and most preferably a 2Ka f less than 5/ e.g., carboxylic acids, and halogenated or perfluorinated carboxylic acids such as acetic, citric and stearic acid, perfluorooctanoic acid, trifluoroacetic acid, dichloroacetic acid, and the like.
Organic derivatives of inorganic acids are also quite useful, such as dioctylphosphoric acid, monobutyl-phosphoric acid, dodecylsulfuric acid, ~3-cyclohexyl-sulfamic acid and the like. Organic acids other than carboxylic acids such as aliphatic and aromatic sulfonic, sulfonylic and phosphonic acids such as bis(per-fluoro-methylsulfonyl)methane are useful. Protonated amine salts such as pyridine hydrochloridel imidazole trifluoro-acetate, aniline methanesulfonate, and the like are suitable acidic substances, as are hydrozines and hydroxyl amine salts such as hydrozine bis-benzene sulfonate.
These and other aspects o~ the present invention may be seen in the following examples.
Example 1 Indolenine Red (10 mgm) was coated out in a polyvinyl alcohol binder (5 g of a 7.5~ by weight aqueous solution) with a molar excess of sodium tetraethylborate onto a polyester film backing in the dark. When the resulting film was inserted into the slide compartment of a commercial slide projector and irradiated, complete bleaching was achieved in less than one second, whereas when sodium tetraphenylborate was used, an irradiation time of over a minute is required. The system was ixed by coating it with a Polaroid~ print coater for black and white prints which contained acetic acid. Subsequent irradiation under the aforementioned conditions resulted in little or no dye bleaching. To date, a shel life of three weeks has been attained with no noticeable loss of bleaching speed. Samples exposed through a dry silver fiche element using standard xenon flashlamps results in an exact reproduction of the fiche element. After fixing in a hydrochloric acid vapor, reader/printer blowback copies were made. Gray scale, resolution and reader/
printer settings were equivalent to dry silver in all respects. The screen image on the reader/printer was an easily readable, brilliant magenta and produced excellent coyies.
Example 2 Samples of the dye tris(2-methyl-4-diethylamino-phenyl~carbenium perfluoro(4-ethylcyclohexane) sulfonate (PECHS) were solution coated at saturated concentrations in a polyvinylacetate binder. The solvent used was a 3:1 (weight) solution of methylethylketone and tolueneO The dye was cationic and a slight molecular excess of the active anion donor sodium tetraethylborate was incorpor-ated into the solution. The air dried coating was stored in the dark and subsequently subjected to varying amounts of focused laser light having a wavelength of 6328 A for several periods of time. Light power density was varied using neutral density filters. Exposure time was controlled by a mechanical shutter with electronic activa-tion. Focused spot size was fixed~ Recorded spot size was found to be a function of optical power density and exposure time. The dye-binder system was then fixed using the following methods: acid vapor exposure (acetic acid for two minutes) or, acid treated paper contact and heat (30 seconds, salicylic acid, 95C). Samples were examined ~66~6;~
microscopically to determine spot size and photomicrographs were taken.
Laser power density was 2.037 x 102 watts/cm2.
Neutral density filters loO~ 2.0, 3.0 and 4.0 were employed to reduce power. Exposure times used were 2/2n where n = 0, 1, 2, . . . 8. The following data were obtained:
N.D. Exposure Spot Diameter Energy Density 10 Filter (sec)_ ( M) (nJ/ m2)
SALT IMAGING SYSTEMS
Field of the I~vention This invention relates to imaging processes and S in particular to dye bleaching image forming systems. A
light sensitive system comprising a dye and a tetra(hydrocarbyl)borate is shown to be capable of being rendered light-insensitive, i.e., fixed, after development.
Bac~round of the Invention There exists a vast array of imaging systems having a multitude of various constructions and composi-tions. Amongst the more widely used systems are silver halide light sensitive systems (including black and white and color photography, dry silver photothermography, instant photography, and diffusion transfer systems, amongst others), photopolymeric sys~ems (including planographic and relief printing plates, photoresist - etching systems, and imaging transfer systems), diazonium color coupling systems, and others. Each system has its own properties attributable to the phenomenon which Eorms the basis of the imaging technology. For example, silver halide imaging systems are noted both for ampli~ication (i.e., image densities which can be increased by further 25 development without additional imagewise exposure) due to the catalytic action of silver towards the reduction of silver ion and for the ~act that light sensitivity may be stopped after development by washing away the light sensitive silver halide salt (i.e., fixing)~ Photo-30 polymeric systems are noted for image stability and easeof application of the imaging layer. Diazonium color coupling systems have high image resolution and are easy to coat onto supporting substrates.
.
One other type of imaging system which has received some attention in recent years uses a salt com-prising an aromatic tetra(hydrocarbyll borate anion as a dye-bleaching or solubility-altering photosensitive compound. U~S. Patent No. 3,567,453 discloses the use of such borate salts (having at least one aryl substituent on the borate) in photoresist and lithographic compositions.
U.S. Patent ~o 3,754,921 discloses an imaging system comprising a leucophthalocyanine and "phenylboronate".
U.S. Paten~ No. 3,716,366 even indicates that image stabilization might be achieved by reaction or dissolution and removal of one of the components (column 5, lines 1-8). British Patents 1,370,058; 1,370,059; 1,370,060;
and 1,386,269 also disclose dye bleaching processes using aromatic borates as light sensitive agents.
U.S. Patent No. 3,716,366 suggests that desensi-tization may be effected by reactions with one of the components to form stable colorless products, and specifically suggests selectively dissolving out one of the components. No specific reagents or reaction mechanisms are suggested for the desensiti~ation proces~, however.
Summary of the Invention It has been found that light sensltive imaging systems having a tetra~hydrocarbyl) borate as a light sensitive component thereoE may be rendered light insensitive, particularly after imaging has been effected, by converting the borate to a product which does not have four carbon-to-boron bonds. The most useful borate containing light sensitive systems comprise a borate and a dye in a binder. Cationic dyes are particularly useful.
11~6~
Detailed Descriptlon o the In~ention Borates are variously reEerred to in the art as borates, boronates, boronides and by other chemical terms, In the practice of the present invention borates are strictly defined as tetra(hydrocarbyl)borates, that ls, a compound having four carbon-to-boron bonds. These compounds may be represented by the formula:
R4 ~1 > B ~ X~
` lO R3 \ R2 wherein Rl, R2, R3, and R4 are independently any groups bonded to the boron from a carbon atom, and X~ is any cation except H~ and boron carbon bond cleaving cations.
The groups Rl, R2, R3, and R4 may be independently selected from such groups as alkyl, aryl, aIkaryl, allyl, arylalkyl, alkenyl, alkynyl, cyano, heterocyclic rings, alkyl-heterocyclic rings, etc. Any group bonded to the boron from a carbon atom is useEul. When these substituents are referred to as groups, i.e., alkyl group versus alkyl, that nomenclature specifically is defined as allowing for substitution on the alkyl moiety ~e.g., ether or thioether linkages in the alkyl chain, halogen, cyano, vinyl, acyloxy, or hydroxy substitution, etc.), remember-ing that the group must be bonded to the boron ~rom acarbon atom. Thus, alkoxy and phenoxy would not be included. Cycloaliphatic groups are included in the definitions, as are heteroayclic groups bonded to the boron from a ring carbon atom or through an alkyl linkage (i.e., alkyl-heterocyclic). It is preferred that the R
groups be selected from aryl (e.g., phenyl or naphthyl groups3, alkyl (e.g., methyl, octyl, stearyl), alkenyl, alkynyl, allyl, and alkaryl (e g., benzyl) groups~
Preferably these groups contain no more than 20 carbon atoms. More preferably they contain no more than 12 carbon atoms and most preferably no more than 8 c~rbon atoms. Cyano is the least preferred aliphatic group.
The more preferred borates are those having at least three aliphatic groups bonded to the boron, and the most pre~erred borates have four aliphatic groups bonded to the boron.
Any cation may be used in association with the borate except for cations which break at least one carbon to boron bond on the borate, e.g., H+. As a standard test, one could limit the cations to those which do not break at least one carbon to boron bond of tetraphenyl-borate. This can be readily determined by standard analytical techniques such as gas chromatography, infrared or mass spectrometry, nuclear magnetic reasonance, etc.
It is highly preerred that the cations, if they are metal cations, be less readily reducible than ferric ions.
Readily reducible metal ions are undeslrable as they tend to fix or react with the borate. Organic cations are preferred. The nature of the cation has not been found to be critical in the practice of the present invention. The most significant contribution of the cation may be its effects upon solubility in different solvents or binders.
The cations may range from simple elemental cations such as alkali metal cations (e.g., Li+, Na~. and K~) to complex cationic dyes and quaternary ammonium cations, e.g., such as represented by the formula:
R8 - N~ - R6 wherein R5, R6, R7, and R8 are independently selected from aliphatic (e.g., alkyl and particularly alkyl of 1 to 12 or preferably 1 to 4 carbon atoms), aryl (e.g., phenyl and naphthyl groups), and aralkyl (e.g., benzyl groups). For example, tetramethyl, tetraethyl, tetrapropyl, tetrabutyl and triethyl-monomethyl ammonium are particularly useful. Ca~ions such as phenyltrimethylammonium and benzyltriethyl-:~66~
ammonium are also quite satisfactory as are phosphoniums and sulfoniums. Quaternary cations in more complex forms such as quaternary dyes and quaternized groups in polymer chains are useful. The polymers, for example, could contain repeating groups such as:
U
CH3/ c~3 b. ~CH2 - CHt [~
N (CH3)3 c. ~CH2 - CHtm ~CH2 - CH~
N ~ N -(CH3) d. tl+ ~ CH2CH2CH2 ~ Nlt+n and e. ~C~2 - CH~
O ~ \~I-CH2 - CH2 - CH2 ~ N(C~3)3 H
wherein m and n represent positive whole integers.
With the proper selection of the quaternary ammonium cations, such polymeric materials could also serve as a binder for the system.
The dyes, for example, may be of any color and any chemical class. These dyes, of course, should not contain groups which would fix or densensitize the borate salts (e.g., carboxylic and groups, sulfonic acid groups, metal ions more readily or as readily reducible than ferric ion). ~ny dye may be used in the practice of the present invention. Specific classes of dyes useful in the practice of the present invention include me~hines, triarylmethanes, cyanines, ketomethylenes, styryls, xanthines, azines, carbocyanines, butadienyls, azomethines, etc. The following are specific examples of dyes used in the practice of the present invention:
~ CH3 CH3 ~
(magenta dye N ~ ~ cation, CH3 CH3 Indolenine Red) ~ ~ CH ~ cation) 2S ~ C ~ N /Cc~3 ~ ~ N\ (cyan dye cation) When cationic dyes have been used, a slight excess of borate anion is desired to provide complete bleaching~
'6~2 `
.
The cationic dyes may have anions other than borates, such as the ionic dyes of the formula:
((C~3C~12~C~ (C~2c~3~2 wherein X is any anion including Cl , I , Br perfluoro(4-ethylperfluorocyclohexane)sulfonate, sulfate, methyl sulfate, methanesulfonate, etc.
R9 and R10 are independently H, alkyl or alkoxy (preferably 1 to 12 carbon atoms and most preferably 1 to 4 carbon atoms), Cl, Br, and I, and Rll is H or alkyl, preferably of 1 to 12 and most preferably 1 to 4 carbon atoms.
Any cationic dye is useful in the practice cf the present lS invention, and their listing is merely cumulative.
Imaging in the light sensitive systems comprising tetrahydrocarbyl borate! dye and binder is effected by irradiation. The radiation which is absorbed by the dye-borate system causes the dye to bleach. A
positive image is thus produced~ The use o~ cationic dyes is believed to spectrally sensitize the borates to radiation absorbed by the dyes associated with the borate.
These are not sensitizing dyes as used in photographic imaging systems tusually in ratios of 1/500 or 1/10,000 of dye to light sensitive agents). These dyes are used in proportions of at least 1/10 to about 1/1 in ratio to the borates. Because the dye-borate system is spectrally sensitive, a multiplicity of colored dyes may be used (e.g., cyan, magenta, and yellow) in the sa~e or different layers.
The binders useful in the present invention must be transparent or at least translucent. According to some practices of the present invention, the layers need not be penetrable by solvents or gases.~ Binders such as natural resins (e.g., gelatin, gum arabic, etc.), synthetic resins ~e.g., polyacrylates, polyvinyl acetals, cellulose esters, polyamides, polycarbonates, polyolefins, polyurethanes, polyepoxides, polyoxyalkylenes, polyvinylhalides, polysi-loxanesl polyvinylacetate, polyvinyl alcohol, etc.), and S other media may be used. The binders may be thermoplastic or highly crosslinked.
The desensitization or fixing of the light sensi-tive tetrahydrocarbyl borates is effected by disrupting a~
least one of the carbon-to-boron bonds so that there are no longer four carbon-to-boron bonds in the compound. The compound may still have four bonds to the boron, but if at least one is no longer a carbon-to-boron bond, the result-ing dye-borate system will not be usefully light sensitive and the resulting image will be stable. The conversion of the borates having four carbon-to-boron bonds to compounds having fewer than four carbon-to-boron bonds can be effected in a variety of fashions. Introducing an acid to reactive association with the tetrahydrocarbyl borate will effect such a conversion. This has been done for example, by subjecting the sheet to hydrochloric acid vapor, coating the sheet lightly with acetic acid, placing an acid containing polymeric sheet in temporary or permanent association with the imaging sheet and heating the composite, or including an acid-releasing light sensitive material in the sheet and irradiating the material (where it is sensitive to a different portion of the spectrum than the dye-borate system). The useful acids include for example, carboxylic acids (e.g., acetic acid, stearic acid, etc.), inorganic acids (e.g., nitric acid, sulfuric acid, hydrobromic acid, hydrochloric acid, sulfamic acid,), and organic acids other than carboxylic acids (e.g., aliphatic sulfonic and sulfonylic acids, fluorinated or perfluorinated carboxylic acids, etc.).
Other materials which may be applied to the sheet in similar fashions include aldehydes (particularly by vapor treatment), peroxides, iodine, readily reducible metal ions, and quinones. These materials need only be g introduced into reactive association ~ith the tetra(hydrocarbyl) borate to ef~ect fixing. Reactive association is defined as such physical proximity between materials as to enable a chemical reaction to take place between themO
The acids and acidic substances useful in the present invention as fixers generally have a PKa of less than 9, preferably a PKa f less than 7, and most preferably a 2Ka f less than 5/ e.g., carboxylic acids, and halogenated or perfluorinated carboxylic acids such as acetic, citric and stearic acid, perfluorooctanoic acid, trifluoroacetic acid, dichloroacetic acid, and the like.
Organic derivatives of inorganic acids are also quite useful, such as dioctylphosphoric acid, monobutyl-phosphoric acid, dodecylsulfuric acid, ~3-cyclohexyl-sulfamic acid and the like. Organic acids other than carboxylic acids such as aliphatic and aromatic sulfonic, sulfonylic and phosphonic acids such as bis(per-fluoro-methylsulfonyl)methane are useful. Protonated amine salts such as pyridine hydrochloridel imidazole trifluoro-acetate, aniline methanesulfonate, and the like are suitable acidic substances, as are hydrozines and hydroxyl amine salts such as hydrozine bis-benzene sulfonate.
These and other aspects o~ the present invention may be seen in the following examples.
Example 1 Indolenine Red (10 mgm) was coated out in a polyvinyl alcohol binder (5 g of a 7.5~ by weight aqueous solution) with a molar excess of sodium tetraethylborate onto a polyester film backing in the dark. When the resulting film was inserted into the slide compartment of a commercial slide projector and irradiated, complete bleaching was achieved in less than one second, whereas when sodium tetraphenylborate was used, an irradiation time of over a minute is required. The system was ixed by coating it with a Polaroid~ print coater for black and white prints which contained acetic acid. Subsequent irradiation under the aforementioned conditions resulted in little or no dye bleaching. To date, a shel life of three weeks has been attained with no noticeable loss of bleaching speed. Samples exposed through a dry silver fiche element using standard xenon flashlamps results in an exact reproduction of the fiche element. After fixing in a hydrochloric acid vapor, reader/printer blowback copies were made. Gray scale, resolution and reader/
printer settings were equivalent to dry silver in all respects. The screen image on the reader/printer was an easily readable, brilliant magenta and produced excellent coyies.
Example 2 Samples of the dye tris(2-methyl-4-diethylamino-phenyl~carbenium perfluoro(4-ethylcyclohexane) sulfonate (PECHS) were solution coated at saturated concentrations in a polyvinylacetate binder. The solvent used was a 3:1 (weight) solution of methylethylketone and tolueneO The dye was cationic and a slight molecular excess of the active anion donor sodium tetraethylborate was incorpor-ated into the solution. The air dried coating was stored in the dark and subsequently subjected to varying amounts of focused laser light having a wavelength of 6328 A for several periods of time. Light power density was varied using neutral density filters. Exposure time was controlled by a mechanical shutter with electronic activa-tion. Focused spot size was fixed~ Recorded spot size was found to be a function of optical power density and exposure time. The dye-binder system was then fixed using the following methods: acid vapor exposure (acetic acid for two minutes) or, acid treated paper contact and heat (30 seconds, salicylic acid, 95C). Samples were examined ~66~6;~
microscopically to determine spot size and photomicrographs were taken.
Laser power density was 2.037 x 102 watts/cm2.
Neutral density filters loO~ 2.0, 3.0 and 4.0 were employed to reduce power. Exposure times used were 2/2n where n = 0, 1, 2, . . . 8. The following data were obtained:
N.D. Exposure Spot Diameter Energy Density 10 Filter (sec)_ ( M) (nJ/ m2)
2.0 0.0625 15.0 1.171
3.0 2.00 25.0 3.869 3.0 l.OG 19.0 1.924 Example 3 A mixture of Indolenine Red-PECHS (100 mg), tetraethylammonium tetrabutylborate (100 mg), and poly-methylacrylate solution (10 ml of a 10~ solids solution in 2-butanone:toluene, 3:1) was coated onto polyester (1.02 x 10-2 cm wet thickness) and the film was allowed ~o dry in the dark overnight.
A. Three samples of this film were imaged through a black target with a clear background on an overhead projector. The first imaged film was placed in a sealed jar above a solution of formaldehyde (50 ml of 37% solution neutralized to pH 8.5 with saturated NaHCO3) for one hour in the dark. Subsequent irradiation by an overhead projector or by room light resulted in little or no dye bleaching.
B. The second imaged sample of this film was placed into a solution of for~aldehyde (50 ml 37% formaldehyde, 2 ml methanol, 0.7 ml saturated NaHCO3) for one hour in the dark Subsequent irradiation by an overhead projector or by room light resulted in little or no dye bleachingO
~12-C. The third imaged sample of this film was placed in a sealed jar above liquid benzaldehyde far one hour.
This procedure fixed the image.
Examples 4-5 Coatings with various binders were prepared using a mixture of 100 mg of Crystal Violet FlOB, 100 mg of Et4N+ BBu4- and lO ml of a binder (10% ~y weight) in MEK-Toluene (3:1). The mixtures were coated on polyester to 1.02 x 10-2 cm wet thickness and dried in the dark.
All films were imaged using an overhead projector through a positive transparency. The developed ~ilms were fixed by dipping them into a CF3C02H solution which contained 0.5% by weight of the acid in perfluoro(tributylamine), an inert fluorochemical solvent. The binders used and the length of time the films were in contact with the acid solution are tabulated. The fixing solution was maintained at room temperature. All ilms fixed and no further bleaching occurred on exposure ~o ambient ligh~.
~;,~æ
Table 2 Binder Time (sec.) a. Rlvacite~ 2009 (a methyl methacrylate homopolymer having a viscosity (cP~
in toluene at 37.5 wt percent at 25C of 1,700) 10 b. Elvacite~ 2041 ~a methyl methacrylate homopolymer having a viscosity ~cP) in toluene at 17.5 wt percent at 25C of 1,400) 15 c. Elvacite~ 2042 ~an ethyl methacrylate homopolymer having a viscosity (cP) in toluene at 37.5 wt percent at 25C of 7,500) 20 d. Elvacite~ 204S (a butyl methacrylate homopolymer having a viscosity (cP) in toluene at 30 wt percent at 25C of 3,600) 20 e. Tyril~ 789 (a styrene-acrylonitrile copolymer) 20 f. Polymethylacrylate 20 The same formulations were utilized with Indolenine Red-PECHS in polyvinylacetate~ as w011 as with azomethine, cyanine, and styryl dyes with comparable results.
~.
A mixture of Indolenine Red-PEC~S (100 mg), tetraethylammonium tetrabutylborate (lO0 mg)~ and polymethylacrylate solution (lO ml of a 10% solids solution in 2-butanone:toluene 3:1) was coated onto polyester (1.02 x 10-2 cm wet thickness). The film was allowed to dry in the dark overnight.
A sample of this film was imaged through a mask on an overhead projector. The film was dipped in a 50%
._, t hydrogen peroxide solution for five minutes. The film was removed, washed with tap water and allowed to dry. At this time the image was fixed.
~ second sample of the Indolenine Red-Et4NBBu4 film was imaged through a mask on an overhead projector.
The film was dipped in a solution containing 1.0 9 benzoyl peroxide, methanol (5 ml), and water (100 ml). The film was removed after 15 minutes in the fixing solution and the image was stabilized.
Ex~mple 7 A mixture of Indolenine Red-PECHS (100 my), tetraethylammonium tetrabutylborate (100 mg), and polymeth~lacrylate (10 ml of a 10~ solids solution in MEK:Toluene, 3:1) was coated onto a polyester film backing (1.016 x lb-2 cm wet thickness) in the dark. The film was allowed to dry overnight. A sample of the dye-bleach film was imaged through a mask using an overhead projector as the exposure source. The film was placed in a jar contain ing a few crystals of iodine and the film was allowed to stand in the dark for 30 minutes. Subsequent irradiation by an overhead projector or room light resulted in little or no further bleaching.
Films of Indolenine Red (15 mg/ml of binder solution), and E~NBBU4 (15 mg/ml of binder) in polyvinylacetate were prepared and dried in the dark.
Three strips of film were imaged and dipped into the solutions listed below for five minutes. The images in all cases were found to be fixed, i.e., stable to light.
Separate solutions (1~ w:v) of p-benzoquinone, methylbenzoquinone, and chlorobenzoquinone in 20 ml water containing 0.5 ml MeOH were prepared.
Examples 9-15 These examples were performed in order to readily show how fixatives may be determined b~ NMR
analysis to determine if a carbon to boron bond has been broken.
A 1% (w/v) solution of Et4NBEt4 was prepared in acetone-d~ and 1/2 ml of this stock solution was weighed into each of 7 NMR tubes. Thus, each tube contained 0.02 mmol of Et4NBEt4. Various fixatives and non-fixatives were added to the NMR tubes (see Table I) and the NMR
spectra were recorded after 3-4 hours at 25C and again a~ter 7 hours at 50G.
TABLE I
Wt. mmol 15 Example Additive Add Additive 9 CH3OH 3.8 mg 0.12 CF3CH2OH 10.3 mg 0.10 11 CH3CO2H 8.4 mg 0~14 12 benzoquinone17.2 mg 0.11 20 13 (CH3)2CO 3/2 H2O13.3 mg 0.14 14 O 9.7 mg 0.11 O~C~o nL~ eJ 0 0 The BEt~ Et ratio was determined for each NMR
spectrum and the results are recorded in Table II.
TABLE II
Example Additive Treatment BEt/ NEt Fixative 9 C~30H 25/3-4 hr. 0.92 No 50/7 hr. 0.93 10 CF3CH2OH 25/3-4 hr. 0 No 50/7 hr. 0 6~
TABLE II (cont.) Tube X Additive Treatment BEt/~Et Fixative 11 CH3C02H 25/3-4 hr. 0.81 Yes 50/7 hr, 0.32 12 benzoquinone25/3-4 hr. 0 Yes 50/7 hr. 0 13 (CF332C0'3/2 H20 25/3-4 hr. 0.95 Yes 50/7 hr. 0.49 14 0 25/3-4 hr. 0.96 No C 50/7 hr. 0.92 O~ ~O
none 25/3-4 hr. 0.96 No 50/7 hr. 0.93 The ratio of BEt4/~Et4 was determined from the ratio of the peak area representing the methylene group of B(CH2CH3)4 relative to that for the methyl group of ~(CH2C~ )4. In the experiments where there was a large decrease in the BEt4 ~ Et4 ratio (e.g., CH3C02~, (CF3)~C0-3/2 H20 and benzoquinone), there was concurrent formation of new peaks in the spectra. These new peaks may be resulting from the formation of new -OCH2CH3 linkages or from the formation of BEt3.
Example 17 The following solution was knife coated in the dark at 1.3 x 10-2 cm wet thickness on a matt paper substrate.
5.0 g polyvinyl acetate (10~ solids in methylethylketone and toluene, 3:1 by weight) 25.0 mg diphenyliodonium tetraphenylborate 28.~ mg allyl triphenyl phosphonium tetraphenylborate 14.0 mg cyan dye -17~
Cl ~ CH=C~-CH=CH-C~= ~ C1 5.0 mg yellow dye CH3 CH3 PECHS
¢~ CH=CH ~3--OCH3 PECHS
2.0 mg magenta dye CH3 OC~3 10~CH=CH43N (CH3) 2 PECHS
After drying in the dark, the sample was exposed in a 500 watt slide projector through ~and in contact with) a 35 mm color positive slide for two ~inutes. A
positive full color reproduction of the original slide resulted.
Fixation was accomplished by soaking five minutes in the following solution:
20f5 parts water 250 ml 5 parts water 1 part methanol 37.5 g phosphotungstic acid The fixed sample was washed five minutes in water to remove any excess acid and allowed to dry~
Following fixing, the resulting full color print was exposed to ambient light for several weeks without showing any deterioration in quality.
1~6s~Z
Example 18 A mixture of polyvinyl acetate (10% solids in methylethylketone and toluene, 3:1 by weight), the magenta dye a~3 ) 2 . CH3 (an amount sufficient to give an optical density of l.0 upon coating and reading with a Kodak status A green filter), and a molar excess of sodium tetraphenyl borate (with respect to the dye), was knife coated in the dark at 7.6 x 10-3 cm wet thickness and air dried in the darkO
The resulting photosensitive film was exposed through a lS positive original using a 500 watt projector to give a positive image. Different samples were fixed by the following procedures:
a) 2 minute exposure to hydrochloric acid vapor b) 2 minute exposure to trifluoroacetic acid vapor c) 2 minute exposure to dichloroacetic acid vapor d) wiping the ~urface o the imaged sample with a solution o dichloroacetic acid in heptane.
Each of the methods of fixincJ yieldecl a stable positive reproduction of the original.
Example 19 A mixture of 5 g fully hydrolyzed polyvinyl alcohol (10~ solids in water) and 50 mg citric acid was knie coated on 7.6 x 10-3 cm polyester at 5.1 x 10-3 cm wet thickness and air dried.
~ second solution containing 5 g of a vinyl 6;Q~
acetate~dibutyl maleate copolymer (81~ vinyl acetate, 19%
dibutylmaleate, as 20~ solids in methylethylketone and toluene, 1:1 by weight~, 10 mg magenta dye ~CH¢H~N (CH3)2 PECHS
13 mg cyan dye ~ C~
N( ~ )2 PECHS , Cl 25 mg yellcw dye lS ~H=CH-~-OCH3 PECHS , and 60 mg sodium tetraphenyl borate was knife coated in the dark on top of the polyvinyl alcohol-acid containing coating and air dried in the dark.
While the sample was heated to 75C, a projected color positive image was focused (using a 500 watt slide projector at approximately two Eeet distance) on the sample. A full color transparency was obtained after ten minutes.
The imaged sample was fixed by heating on a heat blanket at 150~C for 15 seconds and the resulting cop~
was rendered stable to ambient light.
Example 20 Four coatings, each containing a different bleach agent but otherwise being the same, were imaged and subsequently fixed with an exposure to hydrochloric acid vapor for 3-l/2 minutes.
Formulation of the four coatings were as follows:
' ~., 10 ml polyvinyl acetate (15~ solids in methylethylketone and toluene, 1:1 by weight) 100 mg Indolenine Red PECHS , i.e., PECHS
(all four coatings) 10 plus bleach agent:
Coating #1 90.44 mg Et4NBBu4 Coating ~2 95.34 mg Et4NBBu3Phenyl Coating #3 100.5 mg Et4NBBuPhenyl3 Coating #4 83.8 mg NaB(Phenyl)4 The nomenclature for the bleach agents lists the cation first (e.g., Et4N) and then the anion (e.g., BBu4).
Example 21 A mixture of 10 mg of the cyan dye CE~3 (Et2N ~ 3C~Cl-5 g polyvinyl acetate (10% solids in methylethylketone and toluene, 1:1 by weight), and a molar excess (with re.spect to the dye) of sodium tetraethyl borate was knife coated at 7.6 x 10-3 cm wet thickness on polyester and air dried in the dark.
-I A top coating of 3 g Plaskon~ alkyd-vinyl toluene copolyme, 25% solids in VM & P naphtha sold by Amsco Division, Union Oil Company of California, Minneapolis, ~N 554I4) and 100 mg -tetrachlorophthalic acid mono(3,6-dioxa-n-dodecyl) ester was made at 5.1 x 10~3 cm wet thickness. The sample was imaged through a black and white original transparency on an overhead projector for 2 seconds resulting in a~ positive cyan colored image with a clear background. The imaged sample was fixed by heating on a heat blanket for 15 seconds at 90CO
`: :
:' Example 22 An amount of Indolenine Red PECHS dye sufficient to give an optical density (at a film thickness of 1.2 x 10-~ cm) of l.0 when read with a Kodak status A
green filter and a molar excess of sodium tetraethyl borate with respect to the dye, were added to polyvinyl acetate (10% solids in methylethylketone and toluene, 1:1 by weight).
The following, when added to the above solution in a molar excess amount with respect to the sodium tetraethyl borate give fixation after a 10-30 second exposure to a hand-held lamp emitting long wavelength ultraviolet light:
a) methyl-bis-(trichloromethyl)-s-triazine~
b) 3-amino-4-chloro benzophenone-2-carboxylic acid, and c) CC13 CH3O ~ CH=CH- C /W
CCl3 -` Imagewise exposure to the UV source, Eollowed by subsequent intense visible light exposure yields negative rather than positive images~
Generally the dye should constitute from 0.1 to 20 to 40 percent by weight of the imaging layer, preferably from 3 to 30 percent and most preferably from 10 to 25 percent of the imaging layer. The borate generally comprises from 0.1 to 20 or 40 percent by ~eight of the imaging layer, preferably from 2 to 35 percent and more preferably from 10 to 25 percent by weight o~ the imaging layer. The binder generally comprises from 30 or 40 to 99 percent, preferably from 40 to 90 percent and most preferably from 45 to 80 percent by dry weight of the imaging layer.
A. Three samples of this film were imaged through a black target with a clear background on an overhead projector. The first imaged film was placed in a sealed jar above a solution of formaldehyde (50 ml of 37% solution neutralized to pH 8.5 with saturated NaHCO3) for one hour in the dark. Subsequent irradiation by an overhead projector or by room light resulted in little or no dye bleaching.
B. The second imaged sample of this film was placed into a solution of for~aldehyde (50 ml 37% formaldehyde, 2 ml methanol, 0.7 ml saturated NaHCO3) for one hour in the dark Subsequent irradiation by an overhead projector or by room light resulted in little or no dye bleachingO
~12-C. The third imaged sample of this film was placed in a sealed jar above liquid benzaldehyde far one hour.
This procedure fixed the image.
Examples 4-5 Coatings with various binders were prepared using a mixture of 100 mg of Crystal Violet FlOB, 100 mg of Et4N+ BBu4- and lO ml of a binder (10% ~y weight) in MEK-Toluene (3:1). The mixtures were coated on polyester to 1.02 x 10-2 cm wet thickness and dried in the dark.
All films were imaged using an overhead projector through a positive transparency. The developed ~ilms were fixed by dipping them into a CF3C02H solution which contained 0.5% by weight of the acid in perfluoro(tributylamine), an inert fluorochemical solvent. The binders used and the length of time the films were in contact with the acid solution are tabulated. The fixing solution was maintained at room temperature. All ilms fixed and no further bleaching occurred on exposure ~o ambient ligh~.
~;,~æ
Table 2 Binder Time (sec.) a. Rlvacite~ 2009 (a methyl methacrylate homopolymer having a viscosity (cP~
in toluene at 37.5 wt percent at 25C of 1,700) 10 b. Elvacite~ 2041 ~a methyl methacrylate homopolymer having a viscosity ~cP) in toluene at 17.5 wt percent at 25C of 1,400) 15 c. Elvacite~ 2042 ~an ethyl methacrylate homopolymer having a viscosity (cP) in toluene at 37.5 wt percent at 25C of 7,500) 20 d. Elvacite~ 204S (a butyl methacrylate homopolymer having a viscosity (cP) in toluene at 30 wt percent at 25C of 3,600) 20 e. Tyril~ 789 (a styrene-acrylonitrile copolymer) 20 f. Polymethylacrylate 20 The same formulations were utilized with Indolenine Red-PECHS in polyvinylacetate~ as w011 as with azomethine, cyanine, and styryl dyes with comparable results.
~.
A mixture of Indolenine Red-PEC~S (100 mg), tetraethylammonium tetrabutylborate (lO0 mg)~ and polymethylacrylate solution (lO ml of a 10% solids solution in 2-butanone:toluene 3:1) was coated onto polyester (1.02 x 10-2 cm wet thickness). The film was allowed to dry in the dark overnight.
A sample of this film was imaged through a mask on an overhead projector. The film was dipped in a 50%
._, t hydrogen peroxide solution for five minutes. The film was removed, washed with tap water and allowed to dry. At this time the image was fixed.
~ second sample of the Indolenine Red-Et4NBBu4 film was imaged through a mask on an overhead projector.
The film was dipped in a solution containing 1.0 9 benzoyl peroxide, methanol (5 ml), and water (100 ml). The film was removed after 15 minutes in the fixing solution and the image was stabilized.
Ex~mple 7 A mixture of Indolenine Red-PECHS (100 my), tetraethylammonium tetrabutylborate (100 mg), and polymeth~lacrylate (10 ml of a 10~ solids solution in MEK:Toluene, 3:1) was coated onto a polyester film backing (1.016 x lb-2 cm wet thickness) in the dark. The film was allowed to dry overnight. A sample of the dye-bleach film was imaged through a mask using an overhead projector as the exposure source. The film was placed in a jar contain ing a few crystals of iodine and the film was allowed to stand in the dark for 30 minutes. Subsequent irradiation by an overhead projector or room light resulted in little or no further bleaching.
Films of Indolenine Red (15 mg/ml of binder solution), and E~NBBU4 (15 mg/ml of binder) in polyvinylacetate were prepared and dried in the dark.
Three strips of film were imaged and dipped into the solutions listed below for five minutes. The images in all cases were found to be fixed, i.e., stable to light.
Separate solutions (1~ w:v) of p-benzoquinone, methylbenzoquinone, and chlorobenzoquinone in 20 ml water containing 0.5 ml MeOH were prepared.
Examples 9-15 These examples were performed in order to readily show how fixatives may be determined b~ NMR
analysis to determine if a carbon to boron bond has been broken.
A 1% (w/v) solution of Et4NBEt4 was prepared in acetone-d~ and 1/2 ml of this stock solution was weighed into each of 7 NMR tubes. Thus, each tube contained 0.02 mmol of Et4NBEt4. Various fixatives and non-fixatives were added to the NMR tubes (see Table I) and the NMR
spectra were recorded after 3-4 hours at 25C and again a~ter 7 hours at 50G.
TABLE I
Wt. mmol 15 Example Additive Add Additive 9 CH3OH 3.8 mg 0.12 CF3CH2OH 10.3 mg 0.10 11 CH3CO2H 8.4 mg 0~14 12 benzoquinone17.2 mg 0.11 20 13 (CH3)2CO 3/2 H2O13.3 mg 0.14 14 O 9.7 mg 0.11 O~C~o nL~ eJ 0 0 The BEt~ Et ratio was determined for each NMR
spectrum and the results are recorded in Table II.
TABLE II
Example Additive Treatment BEt/ NEt Fixative 9 C~30H 25/3-4 hr. 0.92 No 50/7 hr. 0.93 10 CF3CH2OH 25/3-4 hr. 0 No 50/7 hr. 0 6~
TABLE II (cont.) Tube X Additive Treatment BEt/~Et Fixative 11 CH3C02H 25/3-4 hr. 0.81 Yes 50/7 hr, 0.32 12 benzoquinone25/3-4 hr. 0 Yes 50/7 hr. 0 13 (CF332C0'3/2 H20 25/3-4 hr. 0.95 Yes 50/7 hr. 0.49 14 0 25/3-4 hr. 0.96 No C 50/7 hr. 0.92 O~ ~O
none 25/3-4 hr. 0.96 No 50/7 hr. 0.93 The ratio of BEt4/~Et4 was determined from the ratio of the peak area representing the methylene group of B(CH2CH3)4 relative to that for the methyl group of ~(CH2C~ )4. In the experiments where there was a large decrease in the BEt4 ~ Et4 ratio (e.g., CH3C02~, (CF3)~C0-3/2 H20 and benzoquinone), there was concurrent formation of new peaks in the spectra. These new peaks may be resulting from the formation of new -OCH2CH3 linkages or from the formation of BEt3.
Example 17 The following solution was knife coated in the dark at 1.3 x 10-2 cm wet thickness on a matt paper substrate.
5.0 g polyvinyl acetate (10~ solids in methylethylketone and toluene, 3:1 by weight) 25.0 mg diphenyliodonium tetraphenylborate 28.~ mg allyl triphenyl phosphonium tetraphenylborate 14.0 mg cyan dye -17~
Cl ~ CH=C~-CH=CH-C~= ~ C1 5.0 mg yellow dye CH3 CH3 PECHS
¢~ CH=CH ~3--OCH3 PECHS
2.0 mg magenta dye CH3 OC~3 10~CH=CH43N (CH3) 2 PECHS
After drying in the dark, the sample was exposed in a 500 watt slide projector through ~and in contact with) a 35 mm color positive slide for two ~inutes. A
positive full color reproduction of the original slide resulted.
Fixation was accomplished by soaking five minutes in the following solution:
20f5 parts water 250 ml 5 parts water 1 part methanol 37.5 g phosphotungstic acid The fixed sample was washed five minutes in water to remove any excess acid and allowed to dry~
Following fixing, the resulting full color print was exposed to ambient light for several weeks without showing any deterioration in quality.
1~6s~Z
Example 18 A mixture of polyvinyl acetate (10% solids in methylethylketone and toluene, 3:1 by weight), the magenta dye a~3 ) 2 . CH3 (an amount sufficient to give an optical density of l.0 upon coating and reading with a Kodak status A green filter), and a molar excess of sodium tetraphenyl borate (with respect to the dye), was knife coated in the dark at 7.6 x 10-3 cm wet thickness and air dried in the darkO
The resulting photosensitive film was exposed through a lS positive original using a 500 watt projector to give a positive image. Different samples were fixed by the following procedures:
a) 2 minute exposure to hydrochloric acid vapor b) 2 minute exposure to trifluoroacetic acid vapor c) 2 minute exposure to dichloroacetic acid vapor d) wiping the ~urface o the imaged sample with a solution o dichloroacetic acid in heptane.
Each of the methods of fixincJ yieldecl a stable positive reproduction of the original.
Example 19 A mixture of 5 g fully hydrolyzed polyvinyl alcohol (10~ solids in water) and 50 mg citric acid was knie coated on 7.6 x 10-3 cm polyester at 5.1 x 10-3 cm wet thickness and air dried.
~ second solution containing 5 g of a vinyl 6;Q~
acetate~dibutyl maleate copolymer (81~ vinyl acetate, 19%
dibutylmaleate, as 20~ solids in methylethylketone and toluene, 1:1 by weight~, 10 mg magenta dye ~CH¢H~N (CH3)2 PECHS
13 mg cyan dye ~ C~
N( ~ )2 PECHS , Cl 25 mg yellcw dye lS ~H=CH-~-OCH3 PECHS , and 60 mg sodium tetraphenyl borate was knife coated in the dark on top of the polyvinyl alcohol-acid containing coating and air dried in the dark.
While the sample was heated to 75C, a projected color positive image was focused (using a 500 watt slide projector at approximately two Eeet distance) on the sample. A full color transparency was obtained after ten minutes.
The imaged sample was fixed by heating on a heat blanket at 150~C for 15 seconds and the resulting cop~
was rendered stable to ambient light.
Example 20 Four coatings, each containing a different bleach agent but otherwise being the same, were imaged and subsequently fixed with an exposure to hydrochloric acid vapor for 3-l/2 minutes.
Formulation of the four coatings were as follows:
' ~., 10 ml polyvinyl acetate (15~ solids in methylethylketone and toluene, 1:1 by weight) 100 mg Indolenine Red PECHS , i.e., PECHS
(all four coatings) 10 plus bleach agent:
Coating #1 90.44 mg Et4NBBu4 Coating ~2 95.34 mg Et4NBBu3Phenyl Coating #3 100.5 mg Et4NBBuPhenyl3 Coating #4 83.8 mg NaB(Phenyl)4 The nomenclature for the bleach agents lists the cation first (e.g., Et4N) and then the anion (e.g., BBu4).
Example 21 A mixture of 10 mg of the cyan dye CE~3 (Et2N ~ 3C~Cl-5 g polyvinyl acetate (10% solids in methylethylketone and toluene, 1:1 by weight), and a molar excess (with re.spect to the dye) of sodium tetraethyl borate was knife coated at 7.6 x 10-3 cm wet thickness on polyester and air dried in the dark.
-I A top coating of 3 g Plaskon~ alkyd-vinyl toluene copolyme, 25% solids in VM & P naphtha sold by Amsco Division, Union Oil Company of California, Minneapolis, ~N 554I4) and 100 mg -tetrachlorophthalic acid mono(3,6-dioxa-n-dodecyl) ester was made at 5.1 x 10~3 cm wet thickness. The sample was imaged through a black and white original transparency on an overhead projector for 2 seconds resulting in a~ positive cyan colored image with a clear background. The imaged sample was fixed by heating on a heat blanket for 15 seconds at 90CO
`: :
:' Example 22 An amount of Indolenine Red PECHS dye sufficient to give an optical density (at a film thickness of 1.2 x 10-~ cm) of l.0 when read with a Kodak status A
green filter and a molar excess of sodium tetraethyl borate with respect to the dye, were added to polyvinyl acetate (10% solids in methylethylketone and toluene, 1:1 by weight).
The following, when added to the above solution in a molar excess amount with respect to the sodium tetraethyl borate give fixation after a 10-30 second exposure to a hand-held lamp emitting long wavelength ultraviolet light:
a) methyl-bis-(trichloromethyl)-s-triazine~
b) 3-amino-4-chloro benzophenone-2-carboxylic acid, and c) CC13 CH3O ~ CH=CH- C /W
CCl3 -` Imagewise exposure to the UV source, Eollowed by subsequent intense visible light exposure yields negative rather than positive images~
Generally the dye should constitute from 0.1 to 20 to 40 percent by weight of the imaging layer, preferably from 3 to 30 percent and most preferably from 10 to 25 percent of the imaging layer. The borate generally comprises from 0.1 to 20 or 40 percent by ~eight of the imaging layer, preferably from 2 to 35 percent and more preferably from 10 to 25 percent by weight o~ the imaging layer. The binder generally comprises from 30 or 40 to 99 percent, preferably from 40 to 90 percent and most preferably from 45 to 80 percent by dry weight of the imaging layer.
Claims (50)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for desensitizing a radiation sensitive imaging system comprising a dye and a tetra(hydrocarbyl)borate in a binder which method comprises converting the tetra(hydrocarbyl)borate to a compound having fewer than four carbon-to-boron bonds.
2. The method of claim 1 wherein said conversation is effected by introducing an acid into reactive association with said tetra(hydrocarbyl)bor-ate.
3. The method of claim 2 wherein said acid is selected from the group consisting of inorganic acids, carboxylic acids, aliphatic sulfonic acids, aliphatic sulfonylic acids, and fluorinated carboxylic acids.
4. The method of claim 1 wherein said conversion is effected by introducing an aldehyde into reactive association with said tetra(hydrocarbyl)-borate.
5. The method of claim 1 wherein said conversion is effected by introducing a peroxide into reactive association with said tetra(hydrocarbyl)-borate.
6. The method of claim 1 wherein said conversion is effected by introducing a quinone into reactive association with said tetra(hydrocarbyl)-borate.
7. The method of claim 1 wherein said conversion is effected by introducing iodine into reactive association with said tetra(hydrocarbyl)borate.
8. The method of claim 1 wherein said conversion is effected by introducing readily reducible metal ions into reactive association with said tetra(hydrocarbyl)borate.
9. The method of claim 1, 2 or 3 wherein the dye associated with said tetra(hydrocarbyl)borate is a cationic dye.
10. The method of claim 4, 5 or 6 wherein the dye associated with said tetra(hydrocarbyl)borate is a cationic dye.
11. The method of claim 7 wherein the dye associated with said tetra-(hydrocarbyl)borate is a cationic dye.
12. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms, and X? is any cation except those which break at least one carbon to boron bond of the borate.
13. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms, and X? is any cation except those which break at least one carbon to boron bond of the borate.
14. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms, and X? is any cation except those which break at least one carbon to boron bond of the borate.
15. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the formula X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms, and X? is any cation except those which break at least one carbon to boron bond of the borate, and the dye associated with the tetra-(hydrocarbyl)borate is a cationic dye.
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms, and X? is any cation except those which break at least one carbon to boron bond of the borate, and the dye associated with the tetra-(hydrocarbyl)borate is a cationic dye.
16. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, and X? is any cation except those which break at least one carbon to boron bond of the borate.
17. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, and X? is any cation except those which break at least one carbon to boron bond of the borate.
18. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, and X? is any cation except those which break at least one carbon to boron bond of the borate.
19. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups and X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)-borate is a cationic dye.
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups and X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)-borate is a cationic dye.
20. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups and X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)-borate is a cationic dye.
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups and X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)-borate is a cationic dye.
21. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups and X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)-borate is a cationic dye.
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups and X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)-borate is a cationic dye.
22. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each, and X? is any cation except those which break at least one carbon to boron bond of the borate.
23. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each, and X? is any cation except those which break at least one carbon to boron bond of the borate.
24. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each, and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each, and X? is any cation except those which break at least one carbon to boron bond of the borate.
25. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
26. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and -the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and -the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
27. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
and wherein R1, R2, R3 and R4 are independently selected from the group consist-ing of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
28. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R , R2, R3 and R4 have no more than 20 carbon atoms each and wherein X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R , R2, R3 and R4 have no more than 20 carbon atoms each and wherein X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
29. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the structural formula X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group conslstirlg of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and wherein X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently selected from the group conslstirlg of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and wherein X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
30. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the structural formula X?
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently sel.ected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and wherein X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
wherein R1, R2, R3 and R4 are independently groups bonded to the boron from carbon atoms and are independently sel.ected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and wherein X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
31. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the formula X?
and R1, R2, R3 and R4 are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
and R1, R2, R3 and R4 are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
32. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the formula X?
and R1, R2, R3 and R4 are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
and R1, R2, R3 and R4 are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl-heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
33. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the formula X?
and R1, R2, R3 and R4 are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
and R1, R2, R3 and R4 are independently selected from the group consisting of alkyl groups, aryl groups, alkaryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, cyano, heterocyclic groups, and alkyl heterocyclic groups, wherein R1, R2, R3 and R4 have no more than 20 carbon atoms each and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
34. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are selected from the group consisting of alkyl and allyl groups, X? is any cation except those which break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydro-carbyl)borate is a cationic dye.
and wherein R1, R2, R3 and R4 are selected from the group consisting of alkyl and allyl groups, X? is any cation except those which break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydro-carbyl)borate is a cationic dye.
35. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are selected from the group consisting of alkyl and allyl groups, X? is any cation except those which break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydro-carbyl)borate is a cationic dye.
and wherein R1, R2, R3 and R4 are selected from the group consisting of alkyl and allyl groups, X? is any cation except those which break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydro-carbyl)borate is a cationic dye.
36. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the formula X?
and wherein R1, R2, R3 and R4 are selected from the group consisting of alkyl and allyl groups, X? is any cation except those which break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydro-carbyl)borate is a cationic dye.
and wherein R1, R2, R3 and R4 are selected from the group consisting of alkyl and allyl groups, X? is any cation except those which break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydro-carbyl)borate is a cationic dye.
37. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups bonded to the boron from carbon atoms and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups bonded to the boron from carbon atoms and X? is any cation except those which break at least one carbon to boron bond of the borate.
38. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups bonded to the boron from carbon atoms and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups bonded to the boron from carbon atoms and X? is any cation except those which break at least one carbon to boron bond of the borate.
39. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups bonded to the boron from carbon atoms and X? is any cation except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups bonded to the boron from carbon atoms and X? is any cation except those which break at least one carbon to boron bond of the borate.
40. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the formula X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms each, X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms each, X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
41. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the formula X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms each, X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms each, X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
42. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the formula X?
wherein R1, R2, R3 and R3 are independently alkyl or allyl groups having no more than 20 carbon atoms each, X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
wherein R1, R2, R3 and R3 are independently alkyl or allyl groups having no more than 20 carbon atoms each, X? is any cation except those that break at least one carbon to boron bond of the borate and the dye associated with the tetra(hydrocarbyl)borate is a cationic dye.
43. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms bonded to the boron and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms bonded to the boron and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
44. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms bonded to the boron and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms bonded to the boron and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
45. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the structural formula:
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms bonded to the boron and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl groups having no more than 20 carbon atoms bonded to the boron and X? is a cationic dye except those which break at least one carbon to boron bond of the borate.
46. The method of claim 1, 2 or 3 wherein said tetra(hydrocarbyl)borate has the formula X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl selected groups having no more than 20 carbon atoms, and X? is a cationic dye except those that break at least one carbon to boron bond of the borate.
wherein R1, R2, R3 and R4 are independently alkyl or allyl selected groups having no more than 20 carbon atoms, and X? is a cationic dye except those that break at least one carbon to boron bond of the borate.
47. The method of claim 4, 5 or 6 wherein said tetra(hydrocarbyl)borate has the formula X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl selected groups having no more than 20 carbon atoms, and X? is a cationic dye except those that break at least one carbon to boron bond of the borate.
wherein R1, R2, R3 and R4 are independently alkyl or allyl selected groups having no more than 20 carbon atoms, and X? is a cationic dye except those that break at least one carbon to boron bond of the borate.
48. The method of claim 7 wherein said tetra(hydrocarbyl)borate has the formula X?
wherein R1, R2, R3 and R4 are independently alkyl or allyl selected groups having no more than 20 carbon atoms, and X? is a cationic dye except those that break at least one carbon to boron bond of the borate.
wherein R1, R2, R3 and R4 are independently alkyl or allyl selected groups having no more than 20 carbon atoms, and X? is a cationic dye except those that break at least one carbon to boron bond of the borate.
49. The method of claim 1 performed after said radiation sensitive imaging system has been image-wise exposed to radiation.
50. The method of claim 1, 2 of 3 wherein said tetra(hydrocarbyl)borate is associated with a cationic dye and wherein said method is performed after said radiation sensitive imaging system has been image-wise exposed to radiation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/152,615 US4343891A (en) | 1980-05-23 | 1980-05-23 | Fixing of tetra (hydrocarbyl) borate salt imaging systems |
| US152,615 | 1980-05-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1166062A true CA1166062A (en) | 1984-04-24 |
Family
ID=22543661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000375876A Expired CA1166062A (en) | 1980-05-23 | 1981-04-21 | Fixing of tetra (hydrocarbyl) borate salt imaging systems |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4343891A (en) |
| EP (1) | EP0040978B1 (en) |
| JP (1) | JPS5719737A (en) |
| AU (1) | AU550089B2 (en) |
| BR (1) | BR8103192A (en) |
| CA (1) | CA1166062A (en) |
| DE (1) | DE3165212D1 (en) |
| MX (1) | MX158318A (en) |
| ZA (1) | ZA813472B (en) |
Families Citing this family (125)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4450227A (en) * | 1982-10-25 | 1984-05-22 | Minnesota Mining And Manufacturing Company | Dispersed imaging systems with tetra (hydrocarbyl) borate salts |
| US4447521A (en) * | 1982-10-25 | 1984-05-08 | Minnesota Mining And Manufacturing Company | Fixing of tetra(hydrocarbyl)borate salt imaging systems |
| GB8305134D0 (en) * | 1983-02-24 | 1983-03-30 | Minnesota Mining & Mfg | Radiationsensitive elements |
| US4632895A (en) * | 1984-08-23 | 1986-12-30 | Minnesota Mining And Manufacturing Company | Diffusion or sublimation transfer imaging system |
| US5151520A (en) * | 1985-11-20 | 1992-09-29 | The Mead Corporation | Cationic dye-triarylmonoalkylorate anion complexes |
| US4772541A (en) * | 1985-11-20 | 1988-09-20 | The Mead Corporation | Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same |
| US4937159A (en) * | 1985-11-20 | 1990-06-26 | The Mead Corporation | Photosensitive materials and compositions containing ionic dye compounds as initiators and thiols as autooxidizers |
| US4772530A (en) * | 1986-05-06 | 1988-09-20 | The Mead Corporation | Photosensitive materials containing ionic dye compounds as initiators |
| EP0223587B1 (en) * | 1985-11-20 | 1991-02-13 | The Mead Corporation | Photosensitive materials containing ionic dye compounds as initiators |
| US4800149A (en) * | 1986-10-10 | 1989-01-24 | The Mead Corporation | Photohardenable compositions containing a dye borate complex and photosensitive materials employing the same |
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Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3567453A (en) * | 1967-12-26 | 1971-03-02 | Eastman Kodak Co | Light sensitive compositions for photoresists and lithography |
| DE2007524A1 (en) * | 1970-02-19 | 1971-08-26 | Agfa Gevaert AG, 5090 Leverkusen | Photosensitive materials |
| DE2047250A1 (en) * | 1970-09-25 | 1972-03-30 | Agfa Gevaert AG, 5090 Leverkusen | Photosensitive materials |
| BE793019A (en) * | 1971-12-31 | 1973-06-20 | Agfa Gevaert Nv | METHOD OF MANUFACTURING POSITIVE COLOR IMAGES |
| BE793018A (en) * | 1971-12-31 | 1973-06-20 | Agfa Gevaert Nv | PROCESS FOR THE MANUFACTURE OF POSITIVE COLORED IMAGES |
| BE792967A (en) * | 1971-12-31 | 1973-06-19 | Agfa Gevaert Nv | PROCESS FOR THE MANUFACTURE OF POSITIVE COLOR IMAGES |
| BE792436A (en) * | 1971-12-31 | 1973-06-08 | Agfa Gevaert Nv | PROCESS FOR THE PRODUCTION OF COLORED POSITIVE IMAGES |
-
1980
- 1980-05-23 US US06/152,615 patent/US4343891A/en not_active Expired - Lifetime
-
1981
- 1981-04-21 CA CA000375876A patent/CA1166062A/en not_active Expired
- 1981-05-22 DE DE8181302298T patent/DE3165212D1/en not_active Expired
- 1981-05-22 BR BR8103192A patent/BR8103192A/en not_active IP Right Cessation
- 1981-05-22 JP JP7787981A patent/JPS5719737A/en active Granted
- 1981-05-22 EP EP81302298A patent/EP0040978B1/en not_active Expired
- 1981-05-22 AU AU70954/81A patent/AU550089B2/en not_active Ceased
- 1981-05-22 ZA ZA00813472A patent/ZA813472B/en unknown
- 1981-05-22 MX MX187448A patent/MX158318A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0040978B1 (en) | 1984-08-01 |
| JPS5719737A (en) | 1982-02-02 |
| AU7095481A (en) | 1981-11-26 |
| MX158318A (en) | 1989-01-25 |
| EP0040978A1 (en) | 1981-12-02 |
| BR8103192A (en) | 1982-02-09 |
| JPH0139573B2 (en) | 1989-08-22 |
| AU550089B2 (en) | 1986-03-06 |
| ZA813472B (en) | 1982-07-28 |
| DE3165212D1 (en) | 1984-09-06 |
| US4343891A (en) | 1982-08-10 |
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