US3769016A - Photographic paper for rapid stabilizing process - Google Patents

Photographic paper for rapid stabilizing process Download PDF

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Publication number
US3769016A
US3769016A US00150617A US3769016DA US3769016A US 3769016 A US3769016 A US 3769016A US 00150617 A US00150617 A US 00150617A US 3769016D A US3769016D A US 3769016DA US 3769016 A US3769016 A US 3769016A
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US
United States
Prior art keywords
paper
dye
photographic
photographic paper
stabilizing
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 - Lifetime
Application number
US00150617A
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English (en)
Inventor
A Sato
A Ogawa
J Noguchi
K Ohmura
K Ohkubo
M Hinata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3769016A publication Critical patent/US3769016A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/39—Stabilising, i.e. fixing without washing out

Definitions

  • This invention relates to a photographic paper for a rapid stabilizing process. More specifically, this invention relates to a photographic paper for a rapid stabilizing process which has a high sensitivity to green light in flash exposure and a reduced amount of dye remaining after the stabilization treatment. The terms flash exposure and'remaining of dye will be defined later 2.
  • a xenon flash lamp and a cathode ray tube Two types of light sources, a xenon flash lamp and a cathode ray tube, are used in such equipment.
  • the cathode ray tube those generally known to be used for flying spot which have a fluorescent substance of a short afterglow time are used.
  • fluorescent substances such as those called P-l l, P-IS, P-l6, and P-24" are used. It is known that in an emission spectroscopic energy distribution, a peak exists at 460 nm for P-ll, and at 385 nm for P-16. Since such a distribution corresponds to the spectral sensitivity area inherent to a photosensitive silver halide, the spectral sensitization of photographic materials to be exposed to these fluorescent substances is not particularly necessary.
  • P-lS is known to have a peak at 505 'nm in its emission spectroscopic eri' ergy distribution, and P-24, at 520 nm. Sensitivity to green light needs to be imparted to photographic materials for recording images on such cathode ray tubes.
  • the xenon lamp emits light of a relatively wide range of wavelength. Radiation leaving the light source converges through a condenser lens, a negamatrix, a main lens, a prism, a reflector, or a special lens or prism for letter deformation or other purposes, and forms an image on the light-sensitive surface of a photographic material. Because of the optical system provided in the path of this light, radiation of shorter wavelengths is absorbed to a greater. extent, and the light which has reached the light-sensitive surface contains a reduced proportion of radiation in a range from the ultraviolet to blue, and a larger proportion of green light or radiadescribed information transmitting systems also has an afterglow time much the same as this.
  • flash exposure as used in the present specification, generally refers to such a short time exposure to these light sources. 1
  • Photographic papers used in these information transmitting systems should desirably'be subjected to a rapid processing corresponding to the rapidity of the systems.
  • a rapid processing based on an activator developmentstabilization processing system is frequently used.
  • a silver halide emulsion containing silver chloride such as a pure chloride emulsion, chlorobromide emulsion,
  • the afterglow time of the luminescence of a cathode ray tube is as short as one tenmillionth of a second to one one-hundred thousandth of a second.
  • the xenon flash lamp used in the above is preferred in order to increase the rate of the development.
  • Such an emulsion is poor in spectral sensitization efficiency in comparison with a pure silver bromide emulsion or silver iodobromide emulsion.
  • conventional sensitization dyes have a tendency to reduced efficiency of spectral sensitization in flash exposure.
  • the sensitization dye of the material frequently remains unbleached or is not washed out, in comparison with a photographic material processed through fixation and rinsing steps. It is desired therefore that the sensitization dye used on such a photographic material should be rapidly destroyed and bleached in a stabilization or activator bath.
  • the term remaining of dye refers to the phenomenon in which the sensitization dye remains unbleached after completion of the processing, coloring the surface of a photographic paper.
  • An object of the present invention is to provide a photographic paper for a rapid stabilizing process
  • the object of this invention can be achieved by using a carboxy-alkyl-containing sensitizing dye expressed by the general formula (I) forms an intramolecular salt.
  • a photographic paper coated with a silver halide emulsion containing this sensitizing dye is developed, and then is stabilized with a stabilizing solution containing a sulfurous acid radical or sulfite addition product.
  • the characteristic feature of the chemical structure of the sensitizing dye used in the invention consists in the substituent R
  • R As will be shown later in the Examples, the compound of the formula (III) in which R is an alkyl group imparts good spectral sensitivity to the emulsion but remains to a great extent on photographic paper after the stabilization processing.
  • the compound of the formula IV in which R, is a sulfoalkyl group hardly remains after completion of the processing but has a reduced spectral sensitivity. Only when R is a carboxyalkyl group can satisfactory results be obtained both in spectral sensitization and remaining of dye.
  • the sensitizing dyes of this invention exhibit a strong green sensitizing effect not only on a gelatin-silver halide em ulsion but also on one not containing silver chloride. This effect is the same in flash exposure.
  • a photographic material containing such a dye is developed and then stabilized, the color is bleached, and the resulting image has good whiteness.
  • the sensitizing dyes used in the invention enable silver halide photographic emulsions containing them to be sensitized spectrally. Such dyes are particularly useful for widening the spectral sensitive area of a gelatin- -silver halide emulsion, but also can sensitize fully photographic emulsions containing a water-permeable colloid, such as a water-soluble cellulose derivative, polyvinyl alcohol, or other hydrophilic synthetic or natural resin or polymer instead of gelatin.
  • a water-permeable colloid such as a water-soluble cellulose derivative, polyvinyl alcohol, or other hydrophilic synthetic or natural resin or polymer instead of gelatin.
  • a photographic emulsion used for the photographic paper of the invention may be prepared by adding one or several dyes to a photographic emulsion using customary methods. It is the general practice to add the dyes as a solution in a suitable solvent. The concentration of the dye in the emulsion may be varied over a wide range, for example, from 1 to 200 mg per kilogram of the emulsion according to the effect desired. Conventional additives, such as stabilizers, toning agents, hardening agents, wetting agents, antifoggants, plasticizers, development accelerators, and fluorescent whitening agents, may be added further to the emulsion using customary methods in the preparation of the photographic emulsion used in the invention. A developing agent for activator development, for example, hydroquinone, may also be added to the emulsion using customary methods.
  • the photographic emulsion so prepared may be coated on a suitable paper support, such as'a photographic raw paper, a baryta paper, a resin soaked paper or a resin-coated paper, using customary methods.
  • a suitable paper support such as'a photographic raw paper, a baryta paper, a resin soaked paper or a resin-coated paper, using customary methods.
  • a photographic paper which is especially suitable for high speed transmitting and recording of information, which has a high sensitivity in an orthochromatic spectral region of green light and a sufiiciently low sensitivity to red light, and in which the sensitizing dye is readily bleached by the stabilization processing and the resulting image after the processing is free from the remaining of the dye.
  • the photographic paper of the invention should desirably be subjected to the rapid activator development in view of its uses, but may also be developed in the usual 'manner.
  • the stabilizing processing solution used in the invention contains a thiosulfate or thiocyanate usually employed and also a sulfite salt or sulfite addition product (e.g., an adduct of formaldehyde with sulfurous acid).
  • the sensitizing dye expressed by the general formula (I) may be prepared by a known method based on the disclosure appearing in Belgian Patent No. 693,303, for example.
  • EXAMPLE 1 A methanol solution of 0.005 milligram equivalent of the dye having the structure expressed by the formula (II) above was added to 100 g of a photographic emulsion containing a silver halide composed of 50 mole percent silver chloride and 50 mole percent silver bromide (containing 23 milligram equivalents of silver and 12 grams of gelatin). Saponin (0.06 g) as a wetting agent and 0.27 g of formaldehyde as a hardener were further added. The resulting coating solution was coated on a polyethylene-coated paper (the amount of silver coated 1.4 mg/dm).
  • V-Y 50 color glass filter product of Tokyo Shibaura Electric Co., Ltd., Japan
  • Mark VII sensitometer EG & G Company, U.S.A.
  • the accompanying drawing is a graphical representation showing the relationship of the transmittance of the V-Y 50 color glass filter used in the Examples to wavelength of light. As shown in the drawing, this filter absorbs light of wavelengths corresponding to the sensitivity region inherent to silver halide, and allows the transmission of light of wavelengths above about 500 nm which corresponds to the spectral sensitivity region.
  • the exposed sample was developed for 2 minutes at 20C in a developing solution of the following formula tion.
  • the reflection density through a green filter set down by the ASA standard in the densitometry of a color photographic paper was measured.
  • the reflection density of the control sample was set at 0.
  • dye (ll) of the invention has a high sensitivity to green light in flash exposure and little remains after processing.
  • EXAMPLE 2 One hundred grams each of four photographic emulsion s si lver content 45 milligrams equivalenngelatin content 12 g) containing a silver halide composed of 29 mole percent silver chloride, mole percent silver bromide and 1 mole percent silver iodide were prepared. To three of them, 0.012 milligram equivalent each of the three dyes (II), (III) and (IV) was added respectively.
  • Sodium benzinesulfinate (0.2 g) as an antioxidant, 2.3 g of hydroquinone as a developing agent for V activator development, 0.25 g of 4(N,N- diethylamino)-2,6-xylenol hydrochloride as a development accelerator, 0.06 g of saponin as a wetting agent, and 0.24 g of formaldehyde as a gelatin hardener were further added to each of the emulsions.
  • the resulting coating solution was coated on baryta paper (the amount of silver coated 1.6 milligram equivalents/dm
  • the photographic paper so produced was exposed in the same manner as set forth in Example 1, and processed by Industrial Processor C-230 (Fuji Photographic Film Co., Ltd.) using a sodium hydroxide solution having a pH of 13.3 as an activator and a solution containing 250 g/liter of ammonium thiocyanate, and 160 g/liter of an adduct of formaldehyde with sodium bisulfite as a stabilizer.
  • Example 3 The procedure of Example 2 was repeated using photographic emulsions containing a silver halide composed of 98 mole percent silver bromide and 2 mole percent silver iodide (containing .45 milligram equivalents of silver and grams of gelatin per 100 grams of the emulsion). The results obtained are shown in Table 3 below. 1
  • a stabilizing solution containing a sulfurous acid radical-containing compound or a sulfite addition product after exposure and development comprising a photographic paper coated with a silver halide emulsion containing a sensitizing dye having the following general formula wherein each of R and R, is an alkyl group, R is a carboxyalkyl group, n is l or 2, X is 'an anion, and l is l or 2.
  • said stabilizing member is an adduct of formaldehyde with sodium bisulfite.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00150617A 1970-06-05 1971-06-07 Photographic paper for rapid stabilizing process Expired - Lifetime US3769016A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45048547A JPS4932136B1 (enExample) 1970-06-05 1970-06-05

Publications (1)

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US3769016A true US3769016A (en) 1973-10-30

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US (1) US3769016A (enExample)
JP (1) JPS4932136B1 (enExample)
BE (1) BE768186A (enExample)
CA (1) CA975607A (enExample)
DE (1) DE2128313C3 (enExample)
FR (1) FR2096030A5 (enExample)
GB (1) GB1332841A (enExample)
IT (1) IT945881B (enExample)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3212895A (en) * 1960-12-20 1965-10-19 Eastman Kodak Co Stability of rapid-processed photographic materials
US3380828A (en) * 1965-08-02 1968-04-30 Eastman Kodak Co Antistain agents for spectrally sensitized silver halide photographic elements
US3428455A (en) * 1965-05-28 1969-02-18 Eastman Kodak Co Optically sensitized photographic element containing a developing agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3212895A (en) * 1960-12-20 1965-10-19 Eastman Kodak Co Stability of rapid-processed photographic materials
US3428455A (en) * 1965-05-28 1969-02-18 Eastman Kodak Co Optically sensitized photographic element containing a developing agent
US3380828A (en) * 1965-08-02 1968-04-30 Eastman Kodak Co Antistain agents for spectrally sensitized silver halide photographic elements

Also Published As

Publication number Publication date
IT945881B (it) 1973-05-10
DE2128313A1 (de) 1971-12-09
BE768186A (fr) 1971-11-03
DE2128313C3 (de) 1974-02-07
JPS4932136B1 (enExample) 1974-08-28
DE2128313B2 (de) 1973-07-12
CA975607A (en) 1975-10-07
FR2096030A5 (enExample) 1972-02-11
GB1332841A (en) 1973-10-03

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