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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/02—Direct bleach-out processes; Materials therefor; Preparing or processing such materials
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

• This invention is relate-d to n-onsilver photographic elements and more particularly to nonsilver bleachout and printout elements :for photographic reproduction processes.
• Photographic silver halide elements for printout processes are known in the art. Nonsilver photographic elements for printout processing are desired.
• Another object is to provide a nonsilver printout or bleachout element comprising a support coated with a mixture of at least one pyrylium and/or at least one thiapyrlium salt, and an image promoting compound, preferably dispersed in a water-insoluble, water-permeable binder material.
• Another object is to provide nonsilver printout or bleachout elements of our invention which produce images of various colors including substantially neutral colored dye images by using the appropriate pyrylium and/or thiapyrylium salt(s) in making the element.
• Another object is to provide a printout or a bleachout process for producing a nonsilver image in our photographic element comprising the step of exposing such ele ment to a light image, and when desired the step of stabilizing the image by washing the exposed element in water.
• our printout or bleachout elements comprise a suitable support coated wit-h a light-sensitive mixture comprising at least one pyrylium and/or at least one thiapyrylium salt, and an image promoting compound.
• the light-sensitive mixture is dispersed in a water-insoluble water-permeable :binder material.
• the color of the dye image formed in our element upon printout or bleachout is determined by the pyrylium or thiapyrylium salt or salts present in the element.
• Neutral colored dye images are produced by using appropriate mixtures of two or more pyrylium and/or thiapyrylium salts. These .salts may be incorporated in separate layers each containing an image promoting compound or coated together in a single layer with the image promoting compound.
• Support materials used to advantage in our elements include any of the supports used for photographic elements, such as paper, glass, cellulose acetate, cellulose nitrate, the polycarbonates, and other synthetic film-forming resins, coated with a layer of a material, such as, polyethylene, gelatin, etc.
• Silicated grained aluminum sheets are also used to advantage as a support. Wood, ceramics, stone and various metals are also used.
• R R and R may each represent an aliphatic group having from 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, amyl, isoamyl, hexyl, octyl, nonyl, dodecyl, 2,6-diphenylthia-4- pyramylidenemethyl, ethylene, styrylvinylene, styryl, alkoxysty-ryl, diethoxystyryl, dimethylaminostyryl, 1-butyl- 4-p-dimethylaminophenyl 1,3 butadienyl, ,8-et-hyl-4-dimethyl-aminostyryl; an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, octoxy, etc; aryl, such as phenyl, 4-
• dichlorophenyl, etc. azidophenyl, nitrophenyl, etc., aminophenyl, e.g., 4-c1'iethylanrinophenyl, 4-dirnethylamin0- phenyl, etc.
• X is a hetero atom, such as oxygen, sulfur and selenium
• Y is an anionic function, such as, tor example, perchlorate, fluoborate, nitrate, chloride, bromide, chloroaluminate, chloroferrate, sulfate, bisul-fate, sulfacetate, methosul'fate, alkanoates, such as acetate and especially trifiuoroacetate, trichl-oroacetate, etc, aromatic sulfonates, such as p-toluene sulfonate, etc, anions trom aromatic carboxylic acids, such as 'benZ-oate, and especially p-nitr
• 2,6-bis(4-ch1orocarbornethoxyphenyl)-4-phenylpyrylium fluoroborate 2-(p-n-arnyloxyphenyl)-4,6-diphenylpyryl1um perchlorate.
• 2,6-di-m-nitroplienylt-p-nitrophcnylpyrylium perchlorate 2,4-di-p-methoxyphenyl-6-methoxystyryl pyrylium fluoroborate.
• 2,6-bis(p-ethylpl1eny1) -4-(p-pentoxyphenyD- thiapyrylium perchlorate.
• 2-(3,4-diethoxystyryl)-4,6-diphenyl pyrylium perchlorate 4-(p-n-amyloxyphenyl)-2,6-bis (p-ethylphenyD- thiapyrylium perchlorate. 4,6-diphenyl-2-styryl pyrylium perchlorate. 2-phenylbenzo(h) pyrylium ferric chloride.
• the image promoting compounds of our invention are sensitizers that make the pyrylium, thiapyrylium or selenopyrylium salts sensitive to light.
• the preferred sensitizers are compounds that contain a thiooarbony-l group, a mercapto group or a thioether group. Included among the sensitizers are the following representative compounds:
• Benzoylperoxide (](NHCH2CHCH2)2 Diallyl thiourea The mixtures of the pyrylium salt(s), and/ or thiapyrylium salt(s) and image promoting compound are dissolved advantageously for coating in any suitable solvents such as acetone, methoxyethanol, ethoxyethanol, methanol, hexanone, methylcellosolve acetate, ethylacetate, toluene, xylene, chlorobenzene, trichloroethylene, methylenechloride, ethylenechloride, propylene chloride, etc., and various mixtures of these.
• any suitable solvents such as acetone, methoxyethanol, ethoxyethanol, methanol, hexanone, methylcellosolve acetate, ethylacetate, toluene, xylene, chlorobenzene, trichloroethylene, methylenechloride, ethylenechloride
• any solvent can be used that will dissolve the image-forming compounds, e.g., the pyrylium, thiapyrylium or selenopyrylium salt and the image-promoting compound, and the binder when a binder is used.
• the binders used to advantage include any film forming material which is soluble in the solvents that dissolve the image-forming compounds. Included among these binders are cellulose esters, e.g., ethyl-cellulose phth alate, cellulose acetate hydrogen phthalate, cellulose acetate with various amounts of free hydroxyl groups, etc; phthalated polyvinyl acetals With varying amounts of phthalation; synthetic elastomers, e.g., polyvinyl toluene, styrene butadiene resin, copolymers of ethylacrylate and acrylic acid, etc.
• cellulose esters e.g., ethyl-cellulose phth alate, cellulose acetate hydrogen phthalate, cellulose acetate with various amounts of free hydroxyl groups, etc
• phthalated polyvinyl acetals With varying amounts of phthalation
• synthetic elastomers e.g., polyvinyl to
• the preferred binders are water-insoluble water-permeable materials such as cellulose acetate which is from about 20 to about 35% acetylated, and cellulose acetate hydrogen phthalate.
• the light-sensitive composition is coated to advantage on the support by any of the well known coating techniques used in coating photographic elements.
• the coated and dried element is exposed to a light image which, depending upon the particular materials in the light-sensitive layer, produces either a printout or a bleachout image.
• a printout image w mean the formation of a colored image of a different color than the original coating.
• a bleachout image we mean an image formed by the bleaching of the dye in the original coating.
• the printout or bleachout image is formed by exposure, it is stabilized to advantage by treating the lightsensitive layer with water, preferably warm water.
• Example 1 A light-sensitive coating composition having the general formulation:
• the coatings made on the silicated grained aluminum supports were swabbed with a commercial desentizing etch after the warm-water treatment, then the swabbed coatings were hand-inked with commercial lithographic developing ink. Coatings 1, 3, 4, 5, 6, 7, 8, 13, 15, 16, 17 and 19 hydrochloric acid a stable positive print was obtained. Water can also be used to stabilize the image.
• Coatings made of the compositions in which S-diethylpyrylium or thiapyrylium Salt 05 thiourea is substituted for l-a11yl-2-thi0l1rca give simil r Image promoting compound 5 l'esults- Acetone ml 100
• Example 2 was prepared for each of the pyrylium or thiapyrylium
• a light-sensitive coating composition made by dissolvsalts and image promoting compounds listed in Table 2. ing 0.5 g. of 2-(p-amyloxystyryl)-4,6-diphenylpyrylium A portion of each coating composition was flow-coated perchlorate and 0.5 g.
• the following example illustrates how by controlling the exposure time either a negative or a positive bleachout image can be made of a positive transparency.
• Example 4 A composition containing /2 by weight of 2-(p-amyloxystyryl)-4,6-diphenyl pyrylium perchlorate, /2% by weight of 1-allyl-2-thiourea in acetone was flow-coated on polyethylene-coated paper stock and dried. One sample of this coating was exposed to a positive image in a Bruning Copyflex 110 Office Copying Machine at 12 ft./min. then treated with water to produce a good magenta dye negative reproduction of the original. Another sample of this coating was given the same treatment but exposed at 1 -ft./min. instead of 12 ft./min. to produce a good magenta dye positive reproduction of the original image. A study of the image reproduction of a resolving power chart showed that the image reproduced approximately 50 lines per millimeter.
• Example 5 A coating composition containing 0.5 g. of 2,4-diphenyl-6-(3,4-diethoxyetyryl)pyrylium perchlorate, 10.0
• Example 6 Coating compositions containing 2 /2% by weight of N-allyl-N-(fl-hydroxyethyl)thiourea, 5% by weight of cellulose acetate with about 32.5% acetyl content in a 1:1 mixture of acetone-methoxyethanol and by weight of the pyrylium or thiapyrylium salts indicated in Table 3 were coated on a suitable transparent support and dried. The results obtained by exposing samples of these coatings to an original image in a Bruning Copyflex 100 Diazo Copy Machine at the ft./min. indicated, are summarized in Table 3.
• the bleachout was enhanced by substituting N-allyl- N-(;6-hydroxyethyl)thiourea for l-allyl-Z-thiourea, and was also enhanced by increasing the ratio of the allyl thiourea to the pyrylium (or thiapyrylium) salt.
• Example 7 Coatings were made on a suitable support, of compositions containing by weight of 2-(3,4-dicthoxystyryl)- 4,6-dipheny1 pyrylium perchlorate and N-allyl-N'-(;6-hydroxyethyD-thiou-rea at each of the following percents by weight: A, A, 1% and 2%.
• Each of the 4 dried coatings was exposed to an original image for 1 minute using a Signet B Verifax Copier. The magenta image produced was found to show more bleachout as the percent of the thiourea compound in the composition was increased.
• Example 8 A coating made on a suitable support of a composition containing 2-(3.,4-diethoxystyryl)-4,6-diphenyl pyrylium perchlorate and 1% N-ally-N'-(/8-hydroxyethyl) thiourea was dried, image exposed, water-treated, dried and placed over a fluorescent light source for 16 days. One-half of the magenta dye image was protected from the light during the exposure time. A comparison of the two halves of the print showed substantially no fading of the magenta image, however the slight yellowish background seen in the protected half was essentially clear in the exposed half.
• Three colored images are produced by combining differently colored images, such as cyan, magenta and yellow, or red, blue and green, or magenta and green, or red and cyan, etc.
• These dilferently colored images may be made in separate layers on transparent supports which are superimposed in registration to produce the neutral image, or the required color forming systems are coated in a single layer on a support or in separate layers on a support.
• Example 9 A coating composition was made containing the following material:
• salts are selected which when used together in the proper proportions in a light sensitive layer in our element, will produce upon exposure a neutral reproduction of a neutral original image.
• the light-sensitive elements described in the preceding examples are used to advantage for many copying purposes, such as copying documents, or microfilm copies of the documents, making prints from photographic negatives, color transparencies, etc., making corrective masks for photographic printing operations, etc.
• Another use is for making photographic templates on material such as metal stock, wood, plastics, glass, ceramics, stone, etc., as a guide for such operations as cutting, milling, drilling, etc. This is illustrated as follows.
• Example 10 A coating composition containing 0.2 g. of 4,6-diphenyl-Z-(3.,4-diethoxystyryl)pyrylium perchlorate, 0.25
• a print made by exposing an element having a layer containing 2,,3,4,!6-tetraphenylpyrylium fiuoroborate to a Photofiood RFL No. 2 lamp for 6 seconds at 10 inches through an image was found to fiuoresce strongly in areas that had been exposed to the tungsten source. Prior to tungsten light exposure the coating gave only a very slight fluorescence.
• pyrylium and thiapyryrlium salts used to illustrate the invention were prepared in general by the methods described in copen-ding Van Allan, Natale, and Rauner U.S. Ser. No. 146,743, file-d Oct. 23, 1961, now U.S. Patent No. 3,250,615.
• Compound 2 was prepared by condensing p-methoxyacetophenone with benzaldehyde in the presence of boron trifluoride etherate.
• Compound 3 was prepared by treating compound 2 with sodium sulfide.
• Compound 5 was prepared by condensing one molar equivalent of 4-methoxybenzaldehyde with two molar equivalents of 4-ethylacetophenone in the presence of boron trifiuoride etherate.
• Compound 7 was prepared by condensing 2-et'hyl-4,6- diphenylpyrylium perchlorate with 4-amyloxybenzaldehyde.
• Compound 9 was prepared by condensing 4,6-diphenyl- Z-methylpyrylium perchlorate with cinnamoylaldehyde.
• Compound 10 was prepared by condensing acetophenone with p-acetoxy benzaldehyde in the presence of boron trifluoride etherate and treating the product with sodium sulfide, M.P. 278280 C.
• Compound 1 1 was prepared by condensing chalcone with desoxybenzoin in the presence of boron trifluoride etherate, M.P. 230 C.
• Compound 14 was prepared by condensing one molar equivalent of 2-methoxybenzaldehyde with two molar equivalents of acetophenone in the presence of boron trifluoride etherate.
• Compound 15 was prepared by condensing benzalacetophenone with Z-naphthylaldehyde in the presence of boron trifluoride etherate, M.P. 270 C.
• Compound 16 was prepared like 15 but by using 1- naphthylaldehyde, M.P. 265 C.
• Compound 17 was prepared by treating compound 11 with sodium sulfide.
• Compound 18 was prepared by condensing p-fi-carboxymethoxyacetophenone with benzaldehyde in the presence 10 of boron trifiuoride etherate and heating the product with thionyl chloride, M.P. C.
• Compound 19 was prepared from the corresponding fluoroborate described by Van Allan, Natale and Rauner by metathesis with perchloric acid.
• Compound 20 was prepared by treating compound 1 with nitric acid and treating the product with phosphorous oxychloride, M.P. 300 C.
• Compound 21 was prepared by condensing p-methoxyacetophenone with p-methoxybenzaldehyde in the presence of sodium hydroxide and then treating the product with boron trifluoride etherate, M.P. 285 C.
• Compound 22 was prepared by condensing 4-pentoxybenzaldehyde w-ith 4-ethylacetophenone in the presence of phosphorous oxychloride and reacting the product with sodium sulfide.
• Compound 24 was prepared by condensing 4-amyloxybenzaldehyde with 4-ethylacetophenone in the presence of perchloric acid and treating the product with sodium sulfide.
• Compound 25 was prepared by condensing 6-methyl- 2,4-diphenylpyrylium perchloriate with benzaldehyde.
• Compound 26 was prepared by condensing salicylaldehyde with acetophenone in the presence of boron trifluoride and ferric chloride, M.P. 110 C.
• Compound 27 was prepared by condensing resorcinol with benzoylacetone in the presence of saturated HCl and heating the product with anisaldehyde, M.P. 263 C.
• Compound 28 was prepared by condensing p-dimethylaminobenzaldehyde with acetophenone in the presence of sulfuric acid and treating the product by pouring it int-o alcohol containing perchloric acid, M.P. 335 C.
• Compound 29 was prepared by reacting p-ethylacetophenone with acetic anhydride and condensing the product with 2,6-diphenyl-thia-4-pyrone in the presence of perchloric acid, M.P. C.
• Compound 30 was prepared by condensing 4-formyl-lphenyl-ZA-butadiene with acetophenone in the presence of boron trifluoride etherate and then treating with perchloric acid.
• Compound 31 was prepared by condensing acetophenone with dimethylaminobenzaldehyde in the presence of acetic anhydride and sulfuric acid.
• Image promoting agents A, B, C, D, G and H are well known compounds.
• Image promoting compound F 2-hydroxyethylisothiuronium trichloroacetate, was prepared as follows. Four moles of 2-chloroethanol and one mole of thiourea were placed in a one-liter flask and mechanically stirred at between 35 to 50 C. for 105 hours. The resulting solution was cooled and the white crystalline product precipitated with one liter of diethyl ether, and recrystallized from ethanol.
• the printout or bleachout elements of our invention are valuable for use in making copies of documents, pictures, etc. in neutral tones or in various colors.
• the element comprises a support coated with a solution of one or more pyrylium, thiapyrylium or selenopyrylium salts, an image promoting compound with or without a binder.
• the preferred elements having a binder reproduce an image having more than 565 lines per millimeter.
• the image formed is stabilized by rinsing the element in water.
• a light-sensitive photographic element comprising a support having coated thereon at least one layer comprising a mixture of:
• At least one image-forming compound selected from those having the formula:
• R, R and R each represent a group selected from the class consisting of an aliphatic group, an alkoxy group, and an aryl group;
• X is a heteroatom selected from the class consisting of the oxygen atom, the sulfur atom and the selenium atom; and
• Y is an anionic function;
• At least one sensitizing compound that contains a group selected from the class consisting of thiocarbonyl, mercapto, carbonyl peroxide and thioether;
• a light-sensitive photographic element comprising a support having coated thereon a composition comprising 2-(p-n-amyloxyphenyl) 2,6 bis(p-ethylphenyl)thiapyrylium perchlorate, N-allyl-N'-(fl-hydroxyethyl)thiourea as the sole light-sensitive component and cellulose acetate.
• a light-sensitive photographic element comprising a support having coated thereon a composition comprising 4,6-diphenyl-2-styryl pyrylium perchlorate, N-allyl- N-(/3-hydroxyethyl)thiourea as the sole light-sensitive component and cellulose acetate.
• a light-sensitive photographic element comprising a support having coated thereon a composition comprising 2-phenylbenzo[b]pyrylium ferric chloride, N-allyl-N- (fl-hydroxyethyl)-thiourea as the sole light-sensitive component and cellulose acetate.
• a light-sensitive photographic element comprising a support having coated thereon a composition comprising 2- [6-phenylhexatrienyl-( 1,3,5 ]-4,6-diphenyl pyrylium perchlorate, N-allyl-N-(B-hydroxyethyDthiourea as the sole light-sensitive component and cellulose acetate.
• a light-sensitive photographic element comprising a support having coated thereon a composition comprising 4-(p n amyloxyphenyl)-2,6-bis(p-ethylphenyl)thiapyrylium perchlorate, 2-phenylbenzo[b]pyrylium ferric chloride, 2 [6 phenylhexatrienyl(1,3,5)]-4,6-diphenyl pyrylium perchlorate, and N-allyl-N-(,B-hydroxyethyl) thiourea as the sole light-sensitive component.
• a light-sensitive coating composition comprising: (1) at least one image-forming compound selected from those having the formula:
• R, R and R each represents a group selected from the class consisting of an aliphatic group, an alkoxy group, and an aryl group;
• X is a heteroatom selected from the class consisting of the oxygen atom, the sulfur atom and the selenium atom; and
• Y is an anionic function;
• At least one sensitizing compound that contains a group selected from the class consisting of thiocarbonyl, mercapto, carbonyl peroxide and thioether;
• a light-sensitive photographic element comprising a support having coated thereon at least one layer comprising a mixture of:
• At least one image-forming compound selected from those having the formula:
• R, R and R each represents a group selected from the class consisting of an aliphatic group, an alkoxy group, an aryl group;
• X is a heteroatom selected from the class consisting of the oxygen atom, the sulfur atom and the selenium atom; and
• Y is an anionic function;
• At least one sensitizing compound that contains a group selected from the class consisting of thiocarbonyl, mercapto, carbonyl peroxide and thioether.
• the sensitizing compound is selected from the class consisting of 1-al1yl-2-thiourea, s-diethyl thiourea, N-allyl-N-(B-hydroxyethyl)-thiourea, 2,2',2"-nitrilotriethanol, mercaptobenzoic acid, 2-hydroxyethyl, isothiuronium trichloroacetate, benzoylperoxide anddiallyl thiourea
• a process for making a photographic image comprising the steps:
• R, R and R each represents a group selected from the class consisting of an aliphatic group, an alkoxy group, and an aryl group;
• X is a heteroatom selected from the class consisting of the oxygen atom, the sulfur atom and the selenium atom; and
• Y is an anionic function;
• At least one sensitizing compound that contains a group selected from the class consisting of thiocarbonyl, mercapto, carbonyl peroxide and thioether, and

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Cited By (49)

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Citations (7)

• 1963
  • 1963-02-01 US US255691A patent/US3300314A/en not_active Expired - Lifetime
• 1964
  • 1964-01-30 GB GB3946/64A patent/GB1060561A/en not_active Expired
  • 1964-01-31 DE DEP1269A patent/DE1269479B/de active Pending
  • 1964-07-01 BE BE649986A patent/BE649986A/xx unknown

Patent Citations (7)

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