US3725074A - Fogged,direct positive silver halide emulsions containing hydroxyphthalein dyes and sulfonated compounds - Google Patents

Fogged,direct positive silver halide emulsions containing hydroxyphthalein dyes and sulfonated compounds Download PDF

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Publication number
US3725074A
US3725074A US00125992A US3725074DA US3725074A US 3725074 A US3725074 A US 3725074A US 00125992 A US00125992 A US 00125992A US 3725074D A US3725074D A US 3725074DA US 3725074 A US3725074 A US 3725074A
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United States
Prior art keywords
group
phenylene
silver halide
compound
general formula
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Expired - Lifetime
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US00125992A
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English (en)
Inventor
K Yamasue
T Kondo
K Shiba
M Hinata
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/50—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/58—Two sulfur atoms
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/06—Hydroxy derivatives of triarylmethanes in which at least one OH group is bound to an aryl nucleus and their ethers or esters
    • C09B11/08—Phthaleins; Phenolphthaleins; Fluorescein
    • 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
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
    • G03C1/4853—Direct positive emulsions prefogged characterised by the desensitiser polymethine dyes

Definitions

  • X1, X2, X3, X4 and X5 each represents a halogen atom
  • m, n, L, ⁇ and p represent 0 or 1
  • q represents 0, 1, 2, 3 or 4
  • M represents a member selected from the group consisting of a hydrogen atom, an alkali metal atom, NH4, and an alkaline earth metal
  • R1, R2, R3, and R4 each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group, a halogen atom, a heterocyclic nucleus, an alkylthio group, a heterocyclyl
  • M represents a member selected from the group consisting of a hydrogen atom and a cation giving water solubility to said compound; and said A2 being a member selected from the group consistingI of:
  • R1, R2, R3 and R4 is a substitutent containing -SO3M, wherein M is the same as defined above; and a silver halide photohalide photographic emulsion.
  • This invention relates to a silver halide photographic emulsion and more particularly to a direct positive silver halide photographic emulsion.
  • a halogen-substituted hydroxyphthalein dye represented by the following general Formula I is an excellent dye for maintaining the denite maximum density and definite contrast and increasing the sensitivity.
  • the ⁇ ao-called re-reversion becomes alkylthio group (such as a methylthio group or an ethylthio group), an arylthio group (such as a phenylthio group or a tolylthio group), an amino group, an alkylamino group or a substituted alkylamino group (such as a methylamino group, a dimethylamino group, a diethylamino group, a dodecylamino group, a cyclohexyl amino group, a -hydroxyethylamino group, a di-beta-hydroxyethylamino group, or a beta-sulfoethylamino group), an arylamino group or a substituted arylamino group (such as
  • the extent of the occurrence of the re-reversion depends upon the manner in which the silver halide photographic emulsions are prepared, but the occurrence of the phenomenon is particularly severe when a silver halide photographic emulsion is sensitized by the halogen-substituted hydroxyphthalein -dye represented by the abovementioned general Formula I and accordingly the practical use of the dye has been diicult.
  • the above object of this invention can be attained by incorporating a compound represented by the following general Formula II in a direct positive silver halide photographic emulsion sensitized by the halogen-substituted hydroxyphthalein dye represented by the general Formula i mentioned above.
  • R1, R2, R3, and R4 each represents a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group (such as a phenoxyl group, an o-toloxyl group, a p-sulfophenoxyl group or a meta-naphthoxyl group), a halogen atom (such as a chlorin@ atom or a bromne atom), a heterocyclic nucleus, an
  • M represents a hydrogen atom or a cation giving water solubility to the compound
  • the direct positive silver halide photographic emulsion sensitized by the dye of general Formula l is such that the photographic emulsion has a high sensitivity without reducing the maximum density (Dmax) and contrast by the addition of the dye.
  • Dmax maximum density
  • the direct positive silver halide photographic emulsion sensitized by the dye of general Formula I exhibits re-reversion severely and the minimum density (Dmm) is high, such a photographic emulsion has not been employed practically.
  • a densensitizing compound such as pinakryptol yellow
  • a desensitizing compound such as pinakryptol yellow
  • the Dmax is scarcely reduced.
  • such an attempt is accompanied with the defect that the reversal sensitivity is reduced together with the reduction of the formation of the re-reversion and the minimum density.
  • the compound represented by the general Formula II when present together with the dye represented by the general Formula I in the direct positive silver halide emulsion according to the present invention, the maximum density is scarcely reduced and the formation of the re-reversion and the minimum density is also reduced. In addition, the reversal sensitivity does not reduce, but in some cases increases.
  • the compound represented by the general Formula II has almost no desensitizing property to such photographic emulsions and has no influence thereon.
  • the compound of the general Formula II is used together with the dye represented by the general Formula I, the formation of the re-reversion and the minimum density are reduced.
  • the dye represented by the general Formula I and the compound represented by the general Formula II are a solution of each.
  • the solvent for the dye represented by general Formula I there is water, methanol, and ethanol.
  • an alkali such as sodium hydroxide, may be added to the solvent.
  • the eifective amount of the dye shown by the general Formula II to be added to a direct positive silver halide photographic emulsion is 1-200 mg., and preferably 10- 100 mg., per kilogram of the emulsion.
  • the eifective amount of the compound of general Formula II is 5-2,000 mg., and preferably -1,000 mg., per kilogram of the emulsion.
  • the ratio of the compound of the general Formula I to the compound of the general Formula II is from 1/5 to l/50 by weight.
  • a silver salt such as silver chloride, silver bromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide may be used.
  • the emulsiication and the physical ripening of the silver halide photographic emulsion used in this invention may be made in the manner conventionally employed for ordinary photographic emulsions, but a salt of the metal belonging to Group VIII of the Periodic Table, such as an iridium salt or rhodium salt may be added t0 the silver halide emulsion during the precipitation formation or during the physical ripening.
  • a salt of the metal belonging to Group VIII of the Periodic Table such as an iridium salt or rhodium salt may be added t0 the silver halide emulsion during the precipitation formation or during the physical ripening.
  • the silver halide used in the present invention is fogged to the maximum density by light exposure or by a chemical fogging agent.
  • the chemical fogging agent used for such purpose is required to fog the silver halide without imparting any deleterious effect to the silver halide emulsion, and usually thiourea dioxide, stannous chloride, formaldehyde or hydrazine is used. After the fogging operation is nished, the pH and PAg are controlled as the occasion demands.
  • a solution of the dye represented by the general Formula I is first added to a silver halide emulsion and then a solution of the compound represented by the general Formula H is added to the emulsion followed by stirring well. 'Ihe silver halide emulsion is applied to a support
  • the solution of the dye represented by the general Formula II may be added prior to the addition of the solution of the compound shown by the general Formula I, or a mixture of them may be :added to the emulsion.
  • these additives may be added to the silver halide emulsion during ripening after water Washing.
  • ordinary additives such as a wetting agent or a hardening agent, may be added to the silver halide emulsion.
  • the support there may be employed a glass sheet, a cellulose derivative film, a synthetic resin film, a barytacoated paper, a waterproof paper, a laminated paper, etc.
  • FIG. 1 is a graph showing a characteristic curve of a known emulsion.
  • FIG. 2 is a graph showing a characteristic curve of the emulsion according to this invention.
  • the direct positive image obtained by the development was fixed by a fixing solution containing sodium thiosulfate, washed with water and dried. Thereafter, the optical density of the image was measured by means of a desensitometer. The re'sults are shown in Table 1.
  • Whiteughn sensitivity (Relative Maximum Minimum value) (Dum.) (Dumm) consisting of a hydrogen atom, an alkali metal atom, NH4, and an alkaline earth metal; together with at least one compound represented by the general formula:
  • said compound of Formula II i being present in an amount which will not decrease sensitvity.
  • X1, X2, X3 and X4 in general Formula I represent a member selected from the group consisting of bromine and iodine
  • R1, R2, Rs and ⁇ R4 in the general Formula II represent a member selected from the group consisting of an aryloxy group, an arylthio group, an arylamino group and a substituted arylamino group.
  • a silver halide photographic element comprising a support and a layer of the direct positive silver halide emulsion of claim 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00125992A 1970-03-19 1971-03-19 Fogged,direct positive silver halide emulsions containing hydroxyphthalein dyes and sulfonated compounds Expired - Lifetime US3725074A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45023343A JPS4843132B1 (ja) 1970-03-19 1970-03-19

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US3725074A true US3725074A (en) 1973-04-03

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Country Status (7)

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US (1) US3725074A (ja)
JP (1) JPS4843132B1 (ja)
BE (1) BE764588A (ja)
CA (1) CA985557A (ja)
DE (1) DE2113443A1 (ja)
FR (1) FR2084899A5 (ja)
GB (1) GB1308411A (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5294510A (en) * 1990-06-14 1994-03-15 Minolta Camera Kabushiki Kaisha Photosensitive member containing specific coumarin fluorescent bleaching agent
US6143888A (en) * 1996-06-04 2000-11-07 Ciba Specialty Chemicals Corporation Use of triazine-based UVAs for use as quenchers in paper-making processes
US6605420B2 (en) * 2000-08-22 2003-08-12 Fuji Photo Film Co., Ltd. Photographic processing composition containing bistriazinyl arylenediamine derivative

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1427525A (en) * 1972-07-13 1976-03-10 Agfa Gevaert Directpositive silver halide emulsions

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5294510A (en) * 1990-06-14 1994-03-15 Minolta Camera Kabushiki Kaisha Photosensitive member containing specific coumarin fluorescent bleaching agent
US6143888A (en) * 1996-06-04 2000-11-07 Ciba Specialty Chemicals Corporation Use of triazine-based UVAs for use as quenchers in paper-making processes
AU728995B2 (en) * 1996-06-04 2001-01-25 Ciba Specialty Chemicals Holding Inc. Use of triazine-based UVAs for use as quenchers in paper-making processes
CN1081655C (zh) * 1996-06-04 2002-03-27 西巴特殊化学品控股有限公司 三嗪基紫外线吸收剂在造纸工艺中作为猝灭剂的应用
US6605420B2 (en) * 2000-08-22 2003-08-12 Fuji Photo Film Co., Ltd. Photographic processing composition containing bistriazinyl arylenediamine derivative
US6753425B2 (en) 2000-08-22 2004-06-22 Fuji Photo Film Co., Ltd. Photographic processing composition containing bistriazinyl arylenediamine derivative

Also Published As

Publication number Publication date
BE764588A (fr) 1971-08-16
FR2084899A5 (ja) 1971-12-17
JPS4843132B1 (ja) 1973-12-17
GB1308411A (en) 1973-02-21
CA985557A (en) 1976-03-16
DE2113443A1 (de) 1971-09-30

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