US3773515A - Light-sensitive material containing a polyhalogenated hydrocarbon, an n-vinylcarbazole, and a furfurylidene compound as an image enhancer and stabilizer - Google Patents

Light-sensitive material containing a polyhalogenated hydrocarbon, an n-vinylcarbazole, and a furfurylidene compound as an image enhancer and stabilizer Download PDF

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Publication number
US3773515A
US3773515A US00213538A US3773515DA US3773515A US 3773515 A US3773515 A US 3773515A US 00213538 A US00213538 A US 00213538A US 3773515D A US3773515D A US 3773515DA US 3773515 A US3773515 A US 3773515A
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ingredient
light
sensitive material
ratio
amount
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H Yamashita
N Sekikawa
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances

Definitions

  • ABSTRACT A non-silver halide light-sensitive material for dry processing containing (a) polyhalogenated hydrocarbon, (b) N-vinylcarbazole, (c) a furfurylidene compound and optionally at least one of the following; hydroquinone, resorcinol, derivatives thereof, a dye or dye bases.
  • the main problem with such elements is how to fix the element, that is, how to increase the stability of the obtained image and how to remove the light sensitivity remaining at unexposed portions.
  • unexposed portions are desensitized by heating or treating with a solvent after the exposure. Mere heating, however, is not sufficient, and treatment with a solvent requires a long period of time and has defects such as toxicity.
  • a secondary amine is inactivated by the reaction between aromatic amine and carboxylic acid anhydride to remove the remaining light-sensitivity.
  • the anhydride is so liable to be hydrolyzed by moisture in the air that it lacks storage stability.
  • the components (a) and (b) are necessary for the combination of the components (a), (b), (e), namely polyhalogenated hydrocarbon, N-vinylcarbazole, and dye or dye base, thus see U.S. Pat. No. 3,503,745. Further, for the combination of the components (a), (b), (d), namely polyhalogenated hydrocarbon, N- vinylcarbazole, and hydroquinone, resorcin or derivatives see U.S. Pat. No. 3,544,322.
  • the present invention relates to a dry processing non-silver halide light-sensitive material which provides a black stable image and is characterized by the inactivation of unexposed portions by heating. More particularly, it relates to a light-sensitive material having the following composition; (a) polyhalogenated hydrocarbon, (b) N-vinylcarbazole, (c) furfurylidene compound, and optionally at least one of (d) hydroquinone, resorcinol and derivatives thereof and (e) a dye or dye base.
  • ingredients (a) to (e) in the lightsensitive material is believed to be as follows.
  • Ingredient (a) is a photo-activator which produces free radicals or ions by the action of light.
  • the fundamental composition of the light-sensitive material of the present invention is: (a) polyhalogenated hydrocarbon, (b) N-vinylcarbazole, (c) furfurylidene compound, and optionally at least one of (d) hydroquinone, resorcinol and derivatives thereof, and (e) a dye or dye base.
  • the dye produced by the photochemical reaction between carbon tetrabromide and N-vinylcarbazole is unstable, especially lacking light fastness.
  • a sensitive material wherein gelatin is used as a binder there is obtained, immediately after processing, a greenish-blue image with a yellow background, but, in a bright room, the whole turns dark brown, and a brown colored image appears in the background.
  • a light sensitive material comprising carbon tetrabromide and N- vinylcarbazole
  • the present invention has solved these problems.
  • the fogging at the unexposed portions supposedly results from the color reaction between N- vinylcarbazole polymer and carbon tetrabromide to add to the reaction between non-reacted materials.
  • the formation of the N-vinycarbazoles is sufficiently contemplated.
  • the molecular weights are supposed about from thousands to scores. of thousands.
  • the black image can be obtained by dry processing, which will extend the regions of application of such an element.
  • the light-sensitive material of the present invention can be used instead of an usual printing paper comprising silver halide. It has the advantage 5 that the treatment thereof is easy due to the dry processing.
  • the unexposed portions can be desensitized by heating to 70 150C after imagewise exposure.
  • the temperature range is ID from 40 250C, preferably from 70C 150C.
  • the unexposed portions are clear white, and hence fog density is extremely low.
  • the sensitive wave length region is extended to about 700nm.
  • the following polyhalogenated hydrocarbon can be used:
  • R and R represent H, an alkyl group of one to six carbon atoms, aryl, hydroxyalkyl, benzoyl, acetyl or R represents H, alkyl, halogen, or alkoxy, and n represents an integer of l-4.
  • the stabilizing and spectrally sensitizing ingredient (e) there can be used dyes or dye bases (which are converted to a dye by oxidation) such as photographic spectral sensitizing dye materials being in a form selected from a dye form or a dye base form, such as anthraquinone dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, azine dyes, thiazine dyes, cyanine dyes, styryl dyes, etc.
  • dyes or dye bases which are converted to a dye by oxidation
  • photographic spectral sensitizing dye materials being in a form selected from a dye form or a dye base form, such as anthraquinone dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, azine dyes, thiazine dyes, cyanine dyes, styryl dyes, etc.
  • anthraquinone dyes such as alizaline (C15 800), purpurin (C1l037), alizaline cyanin R (Cll064), etc.
  • triphenylmethane dyes such as malachite green (CI4200), crystal violet (C142555), methyl green (C1684), naphthalene green (Cl735), etc.
  • xanthene dyes such as rhodamine B (Cl45l70), eosin (C145380), fuluolesein (C1766), rose bengal (C1777), erythrosin (C1773), etc.
  • acridine dyes such as acridine orange R (CI46005), acridine yellow (C1785), benzo flavine (C1791 acryflavine, etc.
  • azine dyes such as safranine T (C150240), neutral red (C1825), flavinduline O (C18
  • High molecular weight materials can be used as a binder as long as they have a film-forming ability.
  • high molecular weight materials there are water soluble materials such as gelatin, polyvinyl alcohol, casein, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl pyrrolidone, etc., in addition to organic solventsoluble materials such as vinyl polymers, e.g., vinyl chloride, vinylidene chloride, vinyl acetate, etc., acrylate, polystyrene, ethyl cellulose, rubber chloride, vinylidene chlorideacrylonitrile copolymer, cellulose acetate, waxes, and the like.
  • High molecular weight is meant solid film-forming high molecular weight materials.
  • the molecular weight range is 5,000 to 5,000,000, preferably 20,000 to 5 million.
  • Difurfurylidene pentaerythritol 0.1 g are dissolved in this order in 10 ml of 1,2- dichloroethane. Thereafter, a filter paper (made by TOYO KAGAKU SANGYO COMPANY, LTD., No. 4) was dipped thereinto, taken up, then dried to prepare a sensitive material. (The operation was carried out under a red safety lamp for photography. The processes of the imagewise exposure, heating, etc. are also likewise carried out. The same applies to all other Examples.) When the sensitive material thus obtained was imagewise exposed to a 250 W super high pressure mercury lamp for 10 seconds at a distance of 30 cm through a photographic negative image, there was obtained a black image with a yellow background.
  • the image obtained was light grayish green.
  • the image density increased by about 0.3.
  • EXAMPLE 2 In the same manner as in Example 1 using the following furfurylidene azine instead of difurfurylidene pentaerythritol, there was prepared a light-sensitive material, which was imagewise exposed to a 250 W super high pressure mercury lamp for 10 seconds at a distance of 30 cm through photographic negative image, and then heated to 100C to obtain a black image.
  • EXAMPLE 3 An acetone solution containing 5 g of N- vinylcarbazole was added to 50 ml ofa 16 percent gelatin aqueous solution, then. stirred at high speed at a temperature of 70C for 2 minutes with the use of a homomixer (made by TOKUEHU KIKA KOGYO COMPANY, LTD.) to finely diperse the N- vinylcarbazole in the gelatin. Thereafter, dichloroethane solution containing 4 g of carbon tetrabromide and 0.5 g of difurfurylidene pentaerythritol was added thereto and emulsified and dispersed in the same manner. The resulting emulsion was coated onto a baryta paper and dried to prepare a sensitive material, which was imagewise exposed to a 250 W super high pressure mercury lamp for 10 seconds at a distance of 30 cm through a photographic negative image.
  • a homomixer made by TOKUEHU KIKA KOGYO COMPANY
  • Crystal violet 2 mg were dispersed in the same manner as in Example 3 to prepare a sensitive material.
  • the resulting sensitive material was imagewise exposed to a 300 W photographic flood lamp through a filter which transmits light of a wave length longer than 600 nm and through a photographic positive image for sec. Then the element was exposed to a 250 W super high pressure mercury lamp for 10 seconds at a distance of 30 cm to obtain a black image thereon.
  • 4-(P-dimethylaminostyryl)quinoline l g were dispersed in the same way as in Example 3 to prepare a sensitive material.
  • the resulting material was imagewise exposed to a 300 W incandescent lamp through photographic positive image for 0.5 second at a distance of 35 cm, the whole surface thereof was then exposed to a red lamp which emits light of wavelengths longer than 600 nm for 5 seconds and finally surface thereof exposed to a 250 W mercury lamp for 10 seconds at a distance of 30 cm to obtain a black image with a pale yellow background.
  • Example 5 was duplicated except that polyvinyl alcohol was used instead of gelatin. After a processing as in Example 5, there was obtained a black image with a pale yellow background.
  • Dichloroethane 2 ml are disolved in a 15 percent benzene solution of polystyrene.
  • dichloroethane is used in order to dissolve the difurfurylidene pentaerythritol.
  • the resulting solution was coated onto a baryta paper and than dried.
  • the sensitive material thus obtained was imagewise exposed to a 250 W super high pressure mercury lamp through photographic negative image for 10 seconds at a distance of 30 cm, andwas successively exposed to a 375 W infrared lamp for 30 seconds at a distance of 22 cm to obtain a black image thereon with a pale yellow background.
  • a photosensitive material was imagewise exposed to a mercury lamp and an infraredlamp in the same way as in Example 7, there was obtained a blue image. In this case, when exposure to infrared rays was conducted for a long time, the image turned green and finally brown.
  • hydroquinone derivatives hydroquinone, hydroquinone monomethylether, dimethoxybenzene or P-bis(Z-tetrahydropyranyloxy) benzene were used.
  • the photosensitive materials obtained were exposed to a 250 W mercury lamp for 5 seconds at a distance of 30 cm, then heated to C. for 30 seconds to obtain a blackish-brown image thereon with a white background.
  • Example 8 was duplicated except that a resorcinol derivative was used instead of a hydroquinone.
  • a resorcinol derivative As the resorcinol derivatives, resorcinol, 4-ethylresorcinol, resorcinol monobenzoate or phloroglucin were used.
  • the resulting photosensitive materials were imagewise exposed to a mercury lamp and heated in the same manner as in Example 8, and there was thus obtained a blackish-brown image thereon with a white background.
  • Chloroform 2 ml were dissolved in ml of percent ethyl acetate solution of polymethyl methacrylate, a photosensitive material was prepared and processed in the same manner as in Example 7 to obtain a black image with pale polles background.
  • Chloroform 2 ml were dispersed in gelatin to prepare a photosensitive material in the same manner as in Example 3.
  • the resulting photosensitive material was exposed to 250 W super high pressure mercury lamp imagewise at a distance of cm to obtain a black image thereon.
  • EXAMPLE l2 utes to obtain a blackish-brown image thereon with a white background. The unexposed part thereof did not color when left in a bright room.
  • a non-silver halide light-sensitive material for dry processing containing the ingredients (a) polyhalogenated hydrocarbon, )b) N-vinylcarbazole and (c) furfurylidene compound; said ingredient (a) being the compound represented by the following formula:
  • R represents H, X, COOR', or -C(H);; ,.X,,;-
  • R being a hydrogen atom, methyl group or ethyl group
  • X represents Cl, Br or I
  • n and m represent an integer of 2 or 3
  • said ingredient (c) being the compound represented by the following formula:
  • Y and Y' are a hydrogen atom or alkyl group, for the compound represented by the following formula:
  • ingredient (c) being present in an amount effective to increase the developed image density to blacken said image and to stabilize said image to increase its light fastness.
  • non-silver halide light-sensitive material as claimed in claim 1 wherein said material further contains at least one additional compound of the ingredient (d) and ingredient (e); said ingredient (d) being hydroquinone, resorcinol or derivatives thereof, represented by the following formulas:
  • R and R are a hydrogen atom, an alkyl group having one to six carbon atoms, an aryl group, a hydroxyalkyl group, a benzoyl group, an acetyl group or R" represents a hydrogen atom, alkyl group having one to six carbon atoms, hydroxyl group, halogen atom or alkoxyl group and n represents an integer of l to 4, and ingredient (e) being a photographic spectral sensitizing dye material in a dye or a dye base form.
  • the light-sensitive material of claim I further comprising a binder material.
  • the light-sensitive material of claim 5 wherein the ratio of the amount of ingredient (b) to that of ingredient (d) is between 200 to l and l to 2 and the ratio of the amount of ingredient (b) to that of ingredient (e) is between 10 to 1 and 10 to 1.
  • said ingredient (a) is capable of acting as a photoactivator which produces free radicals or ions by the action of light
  • said ingredient (b) is capable of reacting with said free radicals or ions produced by ingredient (a) to produce color
  • said ingredient (c) is capable of stabilizing and increasing the density of an image formed by the reaction of said ingredients (a) and (b).
  • Y and Y represent a hydrogen atom or alkyl group having from one to six carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00213538A 1970-12-29 1971-12-29 Light-sensitive material containing a polyhalogenated hydrocarbon, an n-vinylcarbazole, and a furfurylidene compound as an image enhancer and stabilizer Expired - Lifetime US3773515A (en)

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US (1) US3773515A (en, 2012)
JP (1) JPS5121336B1 (en, 2012)
DE (1) DE2165465A1 (en, 2012)
FR (1) FR2120989A5 (en, 2012)
GB (1) GB1358108A (en, 2012)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904419A (en) * 1972-05-26 1975-09-09 Fuji Photo Film Co Ltd Non-silver salt photosensitive materials
US3907570A (en) * 1974-03-19 1975-09-23 Scott Paper Co Photosensitive material comprising a furfurylidene, a lower haloalkane and poly-n-vinyl carbazole
US3986880A (en) * 1974-08-23 1976-10-19 Horizons Incorporated A Division Of Horizons Research Incorporated Free radical photosensitive materials
US4028108A (en) * 1974-11-12 1977-06-07 Agfa-Gevaert N.V. Free-radical photographic material
US4251619A (en) * 1977-06-08 1981-02-17 Konishiroku Photo Industry Co., Ltd. Process for forming photo-polymeric image
US4272607A (en) * 1976-03-30 1981-06-09 Hitachi Chemical Company, Ltd. Photosensitive resin composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3394395A (en) * 1964-03-12 1968-07-23 Scott Paper Co Photosensitive medium comprising a furfurylidene, a primary aromatic amine and a lower haloalkane
US3544322A (en) * 1966-07-21 1970-12-01 Yoshikazu Yamada Photosensitive dispersion in a hydrophilic binder incorporating a stabilizer
US3697276A (en) * 1971-02-01 1972-10-10 Horizons Research Inc Polyvinylcarbazole photographic systems

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3394395A (en) * 1964-03-12 1968-07-23 Scott Paper Co Photosensitive medium comprising a furfurylidene, a primary aromatic amine and a lower haloalkane
US3544322A (en) * 1966-07-21 1970-12-01 Yoshikazu Yamada Photosensitive dispersion in a hydrophilic binder incorporating a stabilizer
US3697276A (en) * 1971-02-01 1972-10-10 Horizons Research Inc Polyvinylcarbazole photographic systems

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904419A (en) * 1972-05-26 1975-09-09 Fuji Photo Film Co Ltd Non-silver salt photosensitive materials
US3907570A (en) * 1974-03-19 1975-09-23 Scott Paper Co Photosensitive material comprising a furfurylidene, a lower haloalkane and poly-n-vinyl carbazole
US3986880A (en) * 1974-08-23 1976-10-19 Horizons Incorporated A Division Of Horizons Research Incorporated Free radical photosensitive materials
US4028108A (en) * 1974-11-12 1977-06-07 Agfa-Gevaert N.V. Free-radical photographic material
US4272607A (en) * 1976-03-30 1981-06-09 Hitachi Chemical Company, Ltd. Photosensitive resin composition
US4251619A (en) * 1977-06-08 1981-02-17 Konishiroku Photo Industry Co., Ltd. Process for forming photo-polymeric image

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GB1358108A (en) 1974-06-26
JPS5121336B1 (en, 2012) 1976-07-01
FR2120989A5 (en, 2012) 1972-08-18
DE2165465A1 (de) 1972-07-27

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