EP0324426B1 - Verfahren zur Erzeugung von extrem hochkontrastreichen negativen Bildern - Google Patents

Verfahren zur Erzeugung von extrem hochkontrastreichen negativen Bildern Download PDF

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Publication number
EP0324426B1
EP0324426B1 EP89100317A EP89100317A EP0324426B1 EP 0324426 B1 EP0324426 B1 EP 0324426B1 EP 89100317 A EP89100317 A EP 89100317A EP 89100317 A EP89100317 A EP 89100317A EP 0324426 B1 EP0324426 B1 EP 0324426B1
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Prior art keywords
group
substituted
formula
unsubstituted
nitrogen
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French (fr)
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EP0324426A2 (de
EP0324426A3 (en
Inventor
Yoshihiro C/O Fuji Photo Film Co. Ltd. Takagi
Hisashi C/O Fuji Photo Film Co. Ltd. Okada
Morio C/O Fuji Photo Film Co. Ltd. Yagihara
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP63003445A external-priority patent/JPH01179939A/ja
Priority claimed from JP63003446A external-priority patent/JPH01179940A/ja
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Publication of EP0324426A2 publication Critical patent/EP0324426A2/de
Publication of EP0324426A3 publication Critical patent/EP0324426A3/en
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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
    • G03C1/005—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
    • G03C1/061—Hydrazine compounds
    • 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
    • G03C2001/108—Nucleation accelerating compound

Definitions

  • This invention relates to a silver halide photographic material and a process for forming super high contrast negative images. More particularly, the invention relates to a silver halide photographic material for use in a photomechanical process.
  • an image forming system having super high contrast (in particular, a gamma ( G ⁇ ) of at least 10) is required for improving the reproduction of continuous tone by dot images or the reproduction of line images.
  • lith developer For this purpose, a specific developer called “lith developer” has hitherto been used.
  • the lith developer consists of hydroquinone as the developing agent and also contains a sulfite as a preservative in the form of an addition product with formaldehyde, whereby the concentration of free sulfite ions is reduced as low as possible (typically below 0.1 mol/liter). Accordingly, the lith developer is susceptible to air-oxidation and thus cannot be stored for over 3 days.
  • the pH of the developer must be at least 11.0.
  • the developing agent is liable to be oxidized, the pH is liable to deviate by absorbing CO 2 from the air and stable photographic properties are thus not obtained. Accordingly, a process of obtaining super high contrast images in a developer having a high sulfite ion concentration at a pH below 11.0 has been desired.
  • JP-A-61-167939 the term "JP-A” as used herein mean as "unexamined published Japanese patent application”
  • disulfide compounds in JP-A-61-198147 the term "JP-A” as used herein mean as "unexamined published Japanese patent application”
  • amine series compounds in JP-A-60-140340 are disclosed as contrast enhancing agents.
  • a low-speed, light-sensitive material for safelight use employing a hydrazine compound, and containing a water-soluble rhodium salt, is disclosed in JP-A-60-83038 and 60-162246.
  • the addition of a sufficient amount of rhodium salt to increase the sensitivity obstructs the increase of contrast by the hydrazine compound, whereby the desired sufficiently high contrast images are not obtained.
  • JP-A-62 030 243 discloses a silver halide photographic material comprising a support having provided thereon at least one silver halide emulsion layer, wherein said emulsion layer or another layer of the silver halide photographic material provided on the support contains at least one compound represented by the following formula (I) and at least one blocked development restrainer represented by the following formula (II), and a process for forming a super-high contrast negative image comprising imagewise exposing the above-described photographic material to light and developing the exposed material with a developer containing not less than 0.15 mol/l of a sulfite ion and having a pH of from 10.5 to 12.3.
  • A represents an aliphatic group or an aromatic group
  • B represents a formyl group, an acyl group, an alkyl- or arylsulfonyl group, an alkyl- or arylsulfinyl group, a carbamoyl group, an alkoxy- or aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group or a heterocyclic group
  • R 0 and R 1 each represents a hydrogen atom, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group or a substitued or unsubstituted acyl group, with the proviso that at least one of R 0 and R 1 is a hydrogen atom; and B, R 1 and the nitrogen atom to which B and
  • C A - D (II) wherein C A represents a blocking group capable of releasing a development restrainer or a precursor thereof at the time of development processing regardless of the exposure amount; and D represents a development restrainer or a precursor thereof that is bonded to C A via a hetero atom of D.
  • the development processing of this known silver halide photographic material is carried out with a developer having a pH of 11.6.
  • An object of this invention is to provide a process of forming super high contrast images using a developer having a pH of from 9.6 to 11.0 in a system containing a hydrazine compound.
  • Another object of this invention is to provide a process of forming super high contrast images with stable photographic performance using a stable developer.
  • the present invention provides a process for forming super high contrast negative images, which comprises processing a super high contrast negative type silver halide photographic material comprising a support having thereon at least one layer, one of which must be a silver halide emulsion layer, said silver halide emulsion layer or other hydrophilic colloid layer containing at least one hydrazine derivative and at least one nucleation accelerator represented by following formula (Ia) or (Ib) with a developer having a pH of from 9.6 to less than 10.5; M 1 S( ⁇ X) ⁇ n A 3 -B (Ib) wherein Y represents a group adsorbing onto silver halide; A 1 represents a divalent linkage group composed of an atom or an atomic group selected from carbon, nitrogen, oxygen, and sulfur; A 2 represents a divalent linkage group; A 3 represents a linkage group composed of an atom or an atomic group selected from carbon, nitrogen, oxygen, and sulfur; B represents a substituted or unsubstituted amino group
  • Y represents a group which adsorbs onto silver halide as, for example, a nitrogen-containing heterocyclic group.
  • formula (II) When Y represents a nitrogen-containing heterocyclic group, the compound of formula (Ia) is shown by formula (II) wherein l represents 0 or the integer 1; [(A 1 ) ⁇ P A 2 -B] m has the same meaning as in formula (Ia) described above; and Q represents an atomic group necessary for forming a 5-or 6-membered heterocyclic ring composed of members selected from carbon, nitrogen, oxygen, and sulfur.
  • R the condensation product of said 5- or 6-membered ring with a carbon aromatic ring or a heteroaromatic ring;
  • M 2 represents hydrogen, an alkali metal atom, an ammonium group or a group capable of being replaced with hydrogen or an alkali metal atom under alkali conditions.
  • heterocyclic ring formed by Q examples include the indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, and quinolines. These heterocyclic rings may be substituted as indicated below.
  • examples for the alkali metal atom in M 2 are sodium and potassium, for an ammonium group, e.g. trimethylammonium and dimethylbenzylammonium, or for a group capable of being replaced with hydrogen or an alkali metal atom under alkali conditions, e.g. acetyl, cyanoethyl, and methanesulfonylethyl.
  • an ammonium group e.g. trimethylammonium and dimethylbenzylammonium
  • a group capable of being replaced with hydrogen or an alkali metal atom under alkali conditions e.g. acetyl, cyanoethyl, and methanesulfonylethyl.
  • these heterocyclic rings may be substituted by a nitro group, a halogen atom (e.g., chlorine and bromine), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, t-butyl cyanoethyl, methoxyethyl, and methylthioethyl), a substituted or unsubstituted aryl group (e.g., phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, and naphthyl), a substituted or unsubstituted alkenyl group (e.g., allyl), a substituted or unsubstituted aralkyl group (e.g., benzyl, 4-methylbenzyl, and phenethyl), a substituted or
  • Examples of the divalent linkage group shown by A 1 include:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, and n-butyl), a substituted or unsubstituted aryl group (e.g., phenyl and 2-methylphenyl), a substituted or unsubstituted alkenyl group (e.g., propenyl and 1-methylvinyl), or a substituted or unsubstituted aralkyl group (e.g., benzyl and phenethyl).
  • a substituted or unsubstituted alkyl group e.g., methyl, ethyl, propyl, and n-butyl
  • a substituted or unsubstituted aryl group e.g
  • the above divalent structures may be further combined with a straight chain or branched alkylene group preferably having to 1 to 6 carbon atoms and more preferably 1 to 3 carbon atoms (e.g., methylene, ethylene, propylene, butylene, hexylene, and 1-methylethylene) to also comprise A 1 , e.g.
  • a 2 represents a divalent linkage group such as a straight chain or branched alkylene group (e.g., methylene, ethylene propylene, butylene, hexylene, and 1-methylethylene), a straight chain or branched alkenylene group (e.g., vinylene and 1-methylvinylene), a straight chain or branched aralkylene group (e.g., benzylidene), a straight chain or branched arylene group (e.g., phenylene and naphthylene).
  • a straight chain or branched alkylene group e.g., methylene, ethylene propylene, butylene, hexylene, and 1-methylethylene
  • a straight chain or branched alkenylene group e.g., vinylene and 1-methylvinylene
  • a straight chain or branched aralkylene group e.g., benzylidene
  • arylene group e.g.,
  • a 1 and A 2 in formula (II) may be further substituted with the groups represented by A 1 and A 2 .
  • R 11 and R 22 which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl, alkenyl group or aralkyl group having from 1 to 30 carbon atoms and these groups may be straight chain groups (e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl, allyl, 3-butenyl, benzyl, and 1-naphthylmethyl), branched groups (e.g., iso-propyl and t-octyl), or cyclic groups (e.g., cyclohexyl).
  • R 11 and R 22 which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl, alkenyl group or aralkyl group having from 1 to 30 carbon atoms and these groups may be straight chain groups (e.g., methyl, ethy
  • R 11 and R 12 may combine with each other to form a ring which may contain at least one hetero atom (e.g., oxygen, sulfur and nitrogen) so as to form a saturated heterocyclic ring such as pyrrolidyl, piperidyl and morpholino.
  • hetero atom e.g., oxygen, sulfur and nitrogen
  • substituents for R 11 and R 12 include a carboxy group, a sulfo group, a cyano group, a halogen atom (e.g., fluorine, chlorine, and bromine), a hydroxy group, an alkoxycarbonyl group having from 1 to 20 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, and benzyloxycarbonyl), an alkoxy group having from 1 to 20 carbon atoms (e.g., methoxy, ethoxy, benzyloxy, and phenetyloxy), an aryloxy group having not more than 20 carbon atoms (e.g., phenoxy and p-tolyloxy), an acyloxy group having not more than 20 carbon atoms (e.g., acetyloxy and propionyloxy), an acyl group having not more than 20 carbon atoms (e.g., acetyl,
  • the ammonium group shown by B is generally shown by formula (VIII).
  • R 13 , R 14 , and R 15 have the same meaning as R 11 and R 12 in formula (VII) as described above and Z ⁇ represents an anion such as halide ion (e.g., Cl ⁇ , Br ⁇ and I ⁇ ) a sulfonate ion (e.g., trifluoromethanesulfonate ion, p-toluenesulfonate ion, benzenesulfonate ion, and pchlorobenzenesulfonate ion), a sulfate ion (e.g., ethyl sulfate ion and methyl sulfate ions), a prechlorate ion, a tetrafluoroborate ion and
  • q represents the integer 0 or 1 and when the compound forms an intramolecular salt, q
  • B is a 5- or 6-membered ring containing at least one nitrogen atom and the ring may have substituents or may be condensed with another ring.
  • the nitrogen containing heterocyclic ring are an imidazolyl ring, a pyridyl ring, and a thiazolyl ring.
  • the substituent for the amino group can be selected from the aforesaid substituents for R 11 and R 12 in formula (VII). At least one of Z 1 , Z 2 , and Z 3 must have the same meaning as (A 1 ) ⁇ p A 2 -B.
  • heterocyclic rings may be substituted by the substituents applied to the heterocyclic ring shown by Q in formula (II) as described above.
  • the heterocyclic ring shown by X in formula (Ib) described above is a 5- or 6-membered heterocyclic ring containing at least one of nitrogen, oxygen, selenium, and sulfur and may be condensed with a carbon aromatic ring or a hetero aromatic ring.
  • the heterocyclic ring is preferably aromatic and examples thereof are tetrazole, triazole, thiadiazole, oxadiazole, selenadiazole, imidazole, thiazole, oxazole, benzimidazole, benzthiazole, benzoxazole, benzselenazole, and pyrimidine. Among them, tetrazole and thiazole are particularly preferred.
  • heterocyclic rings may be substituted by the same substituents applied to the heterocyclic rings shown by Q in formula (II).
  • the divalent linkage group shown by A 3 in formula (Ib) is a divalent linkage group composed of an atom or an atomic group selected from hydrogen, carbon, nitrogen, oxygen, and sulfur. Examples thereof are those illustrated as the linkage groups of A 1 and A 2 in formula (Ia) and a straight chain or branched alkinylene group (e.g., -CH-C ⁇ C-CH-).
  • the linkage group shown by A 3 may further comprise a linkage group by combinations of A 1 , A 2 and/or an alkinylene group , e.g.,
  • the alkali metal shown by M 1 in formula (Ib) includes Na + , K + , and Li + .
  • the alkaline earth metal shown by M 1 includes Ca ++ , and Mg ++ .
  • the quaternary ammonium salt shown by M 1 has from 4 to 30 carbon atoms and examples thereof include, (CH 3 ) 4 N ⁇ , (C 2 H 5 ) 4 N ⁇ , (C 4 H 9 ) 4 N ⁇ , C 6 H 5 CH 2 N ⁇ (CH 3 ) 3 , and C 16 H 33 N ⁇ (CH 3 ) 3 .
  • examples of the quaternary phosphonium salt include (C 4 H 9 ) 4 P ⁇ , C 16 H 33 P ⁇ (CH 3 ) 3 , and C 6 H 5 CH 2 P ⁇ (CH 3 ) 3 .
  • the group shown by M1 which can be replaced with hydrogen or an alkali metal atom under alkali conditions include an acetyl group, a cyanoethyl group, and a methanesulfonylethyl group.
  • nucleation accelerators shown by formulae (Ia) and (Ib) are readily synthesized by the methods described in Berichte der Deutschen Chemischen Deutschen , 28 , 77(1895), ibid. , 22 , 568 (1889), ibid. , 29 , 2483(1896), Journal of Chemical Society , 1932 , 1806, Journal of The American Chemical Society , 71 , 4000(1949), Advances in Heterocyclic Chemistry , 9, 165(1968), Organic Synthesis , IV, 569(1963), Journal of The American Chemical Society , 45 , 2390(1923), Chemische Berichte , 9 , 465(1976), JP-A-50-37436 and JP-A-51-3231, U.S.
  • Patents 3,295,976, 3,376,310, 2,585,388, and 2,541,9.24, JP-B-40-28496, JP-B-43-41353, JP-B-60-29390, JP-B-60-29391, JP-B-60-133061, and JP-B-61-1431 (the term "JP-B” as used herein means an "examined published Japanese patent application"), US-A-3,106,467, 3,420,670, 2,271,229, 3,137,578, 3,148,066, 3,511,663, 3,060,028, 3,271,154, 3,251,691, 3,598,599, 3,148,066, 3,615,616, 3,420,664, 3,071,465, 2,444,605, 2,444,606, 2,444,607, and 2,935,404, and JP-A-50-89034, JP-A-57-202531, JP-A-57-167023, JP-A-57-164735, JP-A-60-80839,
  • These accelerators may be used singly or in combination thereof.
  • the hydrazine derivative for use in the present invention includes those having a sulfinyl group as described in US-A-4,478,928 and the compound shown by formula (IX).
  • the aliphatic group shown by R 21 in formula (IX) is preferably an aliphatic group having from 1 to 30 carbon atoms.
  • a straight chain, branched, or cyclic alkyl group having from 1 to 20 carbon atoms is preferred.
  • the branched alkyl group may be cyclized so as to form a saturated heterocyclic ring containing at least one hetero atom.
  • the aforesaid alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamido group, and a carbon-amido group.
  • Examples thereof are t-butyl, n-octyl, t-octyl, cyclohexyl, pyrrolidyl, imidazolyl, tetrahydrofuryl, and morpholino.
  • the aromatic group shown by R 21 in formula (IX) is a monocyclic or dicyclic aryl group or an unsaturated heterocyclic group.
  • the unsaturated heterocyclic group may be condensed with a monocyclic or dicyclic aryl group to form a heteroaryl group.
  • Examples thereof are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.
  • the groups having a benzene ring are preferred.
  • R 21 is a particularly preferred aryl group.
  • the aryl group or aromatic group shown by R 21 may be substituted.
  • substituents include a straight chain, branched, or cyclic alkyl group (preferably having from 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or dicyclic ring the alkyl moiety of which has from 1 to 3 carbon atoms), an alkoxy group (preferably having from 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted by an alkyl group having from 1 to 20 carbon atoms), an acylamino group (preferably having from 2 to 30 carbon atoms), a sulfonamido group (preferably having from 1 to 30 carbon atoms) and a ureido group (preferably having from 1 to 30 carbon atoms).
  • R 21 in formula (IX) may have therein a ballast group being usually used to immobilize photographic additives such as couplers, etc.
  • the ballast group is a group having at least 8 carbon atoms and is relatively inert to photographic properties. Examples thereof include an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group.
  • R 21 in formula (IX) may have therein a group for enhancing the adsorption onto the surface of silver halide grains.
  • adsorptive groups include a thiourea group, a heterocyclic thioamido group, a mercaptoheterocyclic group, a triazole group, as disclosed in US-A-4,385,108.
  • particularly preferred compounds of formula (IX) have therein a group which enhances adsorption onto the surface of silver halide grains.
  • adsorptive groups include a thiourea group, a heterocyclic thioamido group, a mercaptoheterocyclic group, and a triazole group as disclosed in US-A-4,385,108.
  • the preferred substituents for the aryl group or aromatic group shown by R 1 include an amido group, a ureido group, and a thiourea group.
  • a sulfonamido group is particularly preferred.
  • the nucleation accelerator and the hydrazine derivative of the present invention are preferably incorporated in a silver halide emulsion layer, but they may also be incorporated in other light-insensitive hydrophilic colloid layers (e.g., protective layer, interlayer, filter layer, and antihalation layer), preferably those adjacent to a silver halide emulsion layer. They may be added in the same layer or different layers.
  • Water soluble compound of formulae(Ia), (Ib) and (IX) may be added to the hydrophilic colloid solution as an aqueous solution thereof. Conversly, when the compound is sparingly soluble in water, the compound may be added thereto as a solution in an organic solvent which is miscible with water.
  • solvent examples include water, methanol, ethanol, acetone, dimethylformamide, and methylcellosolve.
  • solvent examples include water, methanol, ethanol, acetone, dimethylformamide, and methylcellosolve.
  • the optimal amount of the compounds of formula (Ia), (Ib) and (IX) are selected according to the grain size and the halogen composition of the silver halide emulsion, the method and extent of chemical sensitization, the relation -between the layer(s) in which the compounds are incorporated and a silver halide emulsion, and the kind of an antifoggant.
  • the addition amount of the compound of formula (Ia) for use in the present invention is preferably from 5 mg/m 2 to 500 mg/m 2 , and 10 mg/m 2 to 250 mg/m 2 is particularly preferred. Also, the addition amount of the compound of formula (Ib) is preferably from 1 mg/m 2 to 250 mg/m 2 , and 3 mg/m 2 to 150 mg/m 2 is particularly preferred. Furthermore, the addition amount of the compound of formula (IX) is preferably from 1 mg/m 2 to 300 mg/m 2 , and 2 mg/m 2 to 200 mg/m 2 is particularly preferred. Also, the compound of formula (IX) wherein R 21 contains therein a group enhancing the adsorption onto the surface of silver halide grains is preferably added in an amount of from 2 mg/m 2 to 100 mg/m 2 .
  • the photographic emulsion for use in the present invention may contain silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide, or silver chloride, but it is preferred that the silver halide contains at least 50 mol% silver chloride.
  • the silver halide grains in the photographic emulsion may have a regular crystal form such as cubic, octahedral, dodecahedral, and tetradecahedral; an irregular crystal form such as sphere, and tabular; or a composite of these crystal forms.
  • the silver halide grains may be composed of a mixture of grains having various crystal forms.
  • the silver halide grains for use in the present invention may have different phase between the inside and the surface layer thereof or may be composed of a uniform phase throughout the whole grain.
  • a cadmium salt a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or a complex salt thereof, etc.
  • a cadmium salt a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or a complex salt thereof, etc.
  • a silver halide solvent e.g., ammonia, potassium rhodanate, and thioethers and thione compounds as described in US-A-3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, and JP-A-54-155828
  • a silver halide solvent e.g., ammonia, potassium rhodanate, and thioethers and thione compounds as described in US-A-3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, and JP-A-54-155828
  • the silver halide emulsion for use in the present invention may or may not be chemically sensitized.
  • Chemical sensitization for use in the present invention include a sulfur sensitization method using active gelatin or a sulfur-containing compound capable of reacting with silver (e.g., thiosulfates, thioureas, mercapto compounds, and rhodanines); a reduction sensitizing method using a reducing material (e.g., stannous salt, amines, hydrazine derivatives, formamidinesulfinic acid, and silane compounds); a noble metal sensitization method using a metal compound (e.g., gold complex salts and complex salts of noble metals belonging to group VIII of the Periodic Table, such as Pt, Ir, and Pd); or a combination thereof.
  • a sulfur sensitization method using active gelatin or a sulfur-containing compound capable of reacting with silver e.g., thiosulfates, thioureas,
  • the silver halide emulsions for use in this invention can contain various compounds for preventing the formation of fog during the storage and/or photographic processing of the light-sensitive material or for stabilizing photographic performance.
  • antifoggants or stabilizers include azoles (e.g., benzothiazoliums, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (in particular, nitro- or halogen-substituted benzimidazoles)); heterocyclic mercapto compounds (e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (in particular, l-phenyl-5-mercaptotetrazole), and mercaptopyrimidines), the aforesaid heterocyclic mercapto compounds having a water-solubilizing group such as a carboxy group and a
  • the photographic emulsion for use in the present invention may be spectrally sensitized to relatively a long wavelength of blue light, green light, red light, or infrared light using sensitizing dyes.
  • sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, and hemioxonol dyes.
  • the photographic light-sensitive material being processed in the present invention may contain water-soluble dyes in the hydrophilic colloid layer(s) as filter dyes or for irradiation inhibition, etc.
  • dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
  • oxonol dyes, hemioxanol dyes, and merocyanine dyes are particularly useful.
  • the photographic light-sensitive material of the present invention may further contain in the photographic emulsion layer(s) and other hydrophilic colloid layer(s) an inorganic or organic hardening agent.
  • an inorganic or organic hardening agent e.g., active vinyl compounds (e.g., 1,3,5-triacryloyl-hexahydro-s-triazine and 1,3-vinylsulfonyl-2-propanol) and active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine) can be used singly or as a combination thereof.
  • the photographic light-sensitive material of the present invention may further contain in the photographic emulsion layer(s) or other hydrophilic colloid layer(s) various surface active agents.
  • nonionic surface active agents such as saponin (steroid series), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines, polyalkylene glycol alkylamides, and polyethylene oxide addition products of silicone), glycidol derivatives (e.g., alkenyl succinic acid polyglyceride and alkylphenol polyglyceride), aliphatic acid esters of polyhydric alcohols, alkyl esters of saccharide, etc.; anionic surface active agents containing an acid group (e.g., a carboxy group, a sulfo group, a phospho group, a sulfuric acid ester group, and a phosphoric acid este
  • an acid group e.g.,
  • the photographic emulsion layer(s) of the photographic light-sensitive material of the present invention may further contain polyalkylene oxide or the derivatives thereof such as the ethers, esters, amines, etc., thereof, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidone derivatives for increasing sensitivity, contrast, and/or accelerating development.
  • polyalkylene oxide or the derivatives thereof such as the ethers, esters, amines, etc., thereof, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidone derivatives for increasing sensitivity, contrast, and/or accelerating development.
  • gelatin is advantageously used, but other hydrophilic colloids can also be used.
  • hydrophilic high molecular materials such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, dextran, etc. may be used.
  • a stable developer can be used without use of either a conventional infectious developer or a high alkaline developer of about pH 13 as described in US-A-2,419,975.
  • super high contrast negative images are obtained by processing the light-sensitive material in the present invention with a developer containing a sulfite ion at a concentration of at least 0.15 mol/liter and having pH of from 9.6 to less than 10,5.
  • the developing agent which can be used in the process of the present invention and, for example, dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone), and aminophenols (e.g., N-methyl-p-aminophenol) can be used singly or in combination thereof.
  • dihydroxybenzenes e.g., hydroquinone
  • 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone
  • aminophenols e.g., N-methyl-p-aminophenol
  • the silver halide light-sensitive material in the present invention is preferably processed by a developer containing a dihydroxybenzene as the primary developing agent and a 3-pyrazolidone or an aminophenol as an auxiliary developing agent.
  • the developer contain the dihydroxybenzene in the range of from 0.05 to 0.5 mol/liter and the 3-pyrazolidone or aminophenol in the range of less than 0.06 mol/liter.
  • the developing speed can be increased to thus shorten the development time.
  • the developer for use in the present invention may further contain pH buffers such as sulfites, carbonates, borates, and phosphates of an alkali metal or a development inhibitors or antifoggants such as bromides, iodides and organic antifoggants (nitro-indazoles or benzotriazoles are particularly preferred).
  • the developer may contain a water softener, a resolution aid, a toning agent, a development accelerator, a surface active agent (a polyalkylene oxide is particularly preferred), a defoaming agent, a hardening agent, and/or a silver stain inhibitor of films (e.g., 2-mercaptobenzimidazole sulfonic acids).
  • the silver halide light-sensitive material is fixed in the present invention.
  • Ordinary fixing compositions can be employed including thiosulfates, thiocyanates, and organic sulfur compounds which are known to have an effect as fixing agent.
  • the fix solution may contain a water-soluble aluminum salt as a hardening agent.
  • the processing temperature in the process of the present invention is typically from 18°C to 50°C.
  • An automatic processor is preferably used for the photographic processing of the present invention. Even when the total processing time is in the range of from 90 seconds to 120 seconds,, negative photographic characteristics of super high contrast are obtained.
  • the developer for use in the present invention may contain the compound disclosed in JP-A-56-24347 as a silver stain inhibitor. Furthermore, the developer may contain the compound disclosed in JP-A-61-267759 as a resolution aid. Moreover, the developer may further contain the compound disclosed in JP-A-60-93433 or boron compounds disclosed in JP-A-62-186259.
  • a silver chloroiodobromide emulsion (containing 0.1 mol% silver iodide and 30 mol% silver bromide) was prepared using a double jet method as shown below.
  • (NH 4 ) 3 RhCl 6 was added to the aqueous halide solution (containing KBr, NaCl and KI)as a rhodium salt at a concentration of 5x10 -6 mol/mol-Ag.
  • K 3 IrCl 6 was also added to the aqueous halide solution as an iridium salt at a concentration of 4x10 -7 mol/mol-Ag.
  • aqueous halide solution thus prepared and an aqueous silver nitrate solution were added to an aqueous gelatin solution and mixed for 60 minutes at 45°C to provide a mono-dispersed cubic grain size halide having a mean grain size of 0.25 ⁇ m.
  • 1x10 -5 mol/mol-Ag of sodium thiosulfate and 1x10 -5 mol/mol-Ag of potassium chloroaurate were added to the emulsion for gold sensitization.
  • each of IX-9, IX-31, IX-20, IX-32, IX-34, and IX-35 as the hydrazine compound shown by formula (IX) and each of Ia-15 and Ib-7 as a nucleation accelerator as shown in Table 1 below to provide the silver halide emulsion.
  • a coating composition for a protective layer was composed of an aqueous gelatin solution containing gelatin, sodium dodecylbenzenesulfonate, colloidal silica, a dispersion of polyethyl acrylate, polymethyl methacrylate (matting agents), and sodium polystyrenesulfonate (tackifier).
  • the aforesaid emulsion and the coating composition for the protective layer were simultaneously coated on a transparent plastic film support at a gelatin coverage of 1.6 g/m 2 for the protective layer and a silver coverage of 3.6 g/m 2 for the emulsion layer.
  • Each sample thus prepared was exposed to tungsten light of 3200 K through a sensitometric optical wedge for 5 seconds, developed by developer (A) or (D) having the composition shown below for 30 seconds at 38°C, fixed, washed, and dried.
  • An automatic processor FG-660F, made by Fuji Photo Film Co., Ltd. was used for the development processing.
  • Developer (D) was prepared by adding acetic acid to developer (A) reducing the pH to 10.4.
  • Developers (B), (C), (D), (E), (F), and (G) were prepared having the same composition as the developer in Example 1 except that the pH value was adjusted as shown in Table 2.
  • Light-sensitive film prepared as in Sample No. 9 of Example 1 was processed using the developer of Example 1, as adjusted for pH, and the G ⁇ value was then measured. The results are shown in Table 2. After placing one liter of each of the developers (A) to (G) in a one liter beaker and allowing to age at room temperature and open to air for one week, the light-sensitive film was processed using the one week old developer and the G ⁇ value was measured. The results are also shown in Table 2.

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Claims (18)

  1. Verfahren zur Bildung von Negativbildern mit superhohem Kontrast, umfassend das Verarbeiten eines photographischen Silberhalogenidnegativmaterials, umfassend einen Träger mit darauf wenigstens einer Schicht, wobei wenigstens eine davon eine Silberhalogenidemulsionsschicht sein muß, und die Silberhalogenidemulsionsschicht oder andere hydrophile Kolloidschicht wenigstens ein Hydrazinderivat und wenigstens einen durch folgende Formel (Ia) oder (Ib) dargestellten Keimbildungsbeschleuniger enthält, mit einem Entwickler mit einem pH von 9,6 bis weniger als 10,5
    Figure imgb0183

            M1S(̵X)̵nA3-B     (Ib)

    worin bedeuten:
    Y eine auf Silberhalogenid adsorbierende Gruppe; A1 eine zweiwertige Verknüpfungsgruppe, gebildet aus einem Atom oder einer Atomgruppe, ausgewählt aus Kohlenstoff, Stickstoff, Sauerstoff und Schwefel; A2 eine zweiwertige Verknüpfungsgruppe; A3 eine Verknüpfungsgruppe, gebildet aus einem Atom oder einer Atomgruppe, ausgewählt aus Kohlenstoff, Stickstoff, Sauerstoff und Schwefel; B eine substituierte oder nicht-substituierte Aminogruppe, eine Ammoniumgruppe oder einen Stickstoff enthaltenden heterocyclischen Ring; X einen zweiwertigen heterocyclischen Ring, enthaltend Stickstoff, Sauerstoff, Selen oder Schwefel; M1 ein Wasserstoffatom, ein Alkalimetall, ein Erdalkalimetall, ein quaternäres Ammoniumsalz, ein quaternäres Phosphoniumsalz, eine Amidinogruppe; m die ganze Zahl 1, 2 oder 3; und n und p jeweils 0 oder die ganze Zahl 1.
  2. Verfahren nach Anspruch 1, worin die absorbierende Gruppe Y eine Stickstoff enthaltende heterocyclische Gruppe ist, derart, daß der Keimbildungsbeschleuniger durch die Formel
    Figure imgb0184
     dargestellt wird,
    worin bedeuten:
    Q eine Atomgruppe, welche notwendig ist zur Bildung eines 5- oder 6-gliedrigen heterocyclischen Rings, zusammengesetzt aus Bestandteilen, ausgewählt aus Kohlenstoff, Stickstoff, Sauerstoff und Schwefel, oder das Kondensationsprodukt des 5- oder 6-gliedrigen Rings mit einem aromatischen Kohlenstoffring oder einem heteroaromatischen Ring; M2 Wasserstoff, ein Alkalimetallatom, eine Ammoniumgruppe oder eine Gruppe, die durch Wasserstoff oder ein Alkalimetallatom unter alkalischen Bedingungen ersetzt werden kann; und 1 0 oder die ganze Zahl 1.
  3. Verfahren nach Anspruch 2, worin die Stickstoff enthaltende heterocyclische Gruppe ein substituiertes oder nicht-substituiertes Indazol, Benzimidazol, Benzotriazol, Benzoxazol, Benzthiazol, Imidazol, Thiazol, Oxazol, Triazol, Tetrazol, Azainden, Pyrazol, Indol, Triazin, Pyrimidin, Pyridin oder Chinolin umfaßt.
  4. Verfahren nach Anspruch 2, worin die M2-Freisetzungsgruppe Acetyl, Cyanoethyl oder Methansulfonylethyl ist.
  5. Verfahren nach Anspruch 1, worin die zweiwertige Verknüpfungsgruppe A1
    Figure imgb0185
     oder eine Kombination davon
    mit einer geradkettigen oder verzweigtkettigen Alkylengruppe ist, worin R1, R2, R3, R4, R5, R6, R7, R8, R9 und R10 jeweils Wasserstoff, eine substituierte oder nicht-substituierte Alkylgruppe, eine substituierte oder nicht-substituierte Arylgruppe, eine substituierte oder nicht-substituierte Alkenylgruppe oder eine substituierte oder nicht-substituierte Aralkylgruppe bedeuten.
  6. Verfahren nach Anspruch 1, worin die zweiwertige Verknüpfungsgruppe A2 eine geradkettige oder verzweigte Alkylengruppe, eine geradkettige oder verzweigte Alkenylengruppe, eine geradkettige oder verzweigte Aralkylengruppe oder eine geradkettige oder verzweigte Arylengruppe ist.
  7. Verfahren nach Anspruch 1, worin der zweiwertige heterocyclische Ring X ein substituiertes oder nicht-substituiertes Tetrazol, Triazol, Thiadiazol, Oxadiazol, Selenadiazol, Imidazol, Thiazol, Oxazol, Benzimidazol, Benzthiazol, Benzoxazol, Benzselenazol oder Pyrimidin umfaßt.
  8. Verfahren nach Anspruch 1, worin die zweiwertige Verknüpfungsgruppe A3
    Figure imgb0186
     oder eine Kombination davon
    mit einer geradkettigen oder verzweigten Alkylengruppe und/oder einer geradkettigen oder verzweigten Alkinylengruppe ist, worin R1, R2, R3, R4, R5, R6, R7, R8, R9 und R10 jeweils Wasserstoff, eine substituierte oder nicht-substituierte Alkylgruppe, eine substituierte oder nicht-substituierte Arylgruppe, eine substituierte oder nicht-substituierte Alkenylgruppe oder eine substituierte oder nicht-substituierte Aralkylgruppe bedeuten.
  9. Verfahren nach Anspruch 1, worin der Stickstoff enthaltende heterocyclische Ring B Imidazolyl, Pyridyl oder Thiazolyl ist.
  10. Verfahren nach Anspruch 2, worin der Keimbildungsbeschleuniger durch die Formel
    Figure imgb0187
     dargestellt ist.
  11. Verfahren nach Anspruch 2, worin der Keimbildungsbeschleuniger durch die Formel
    Figure imgb0188
     dargestellt ist.
  12. Verfahren nach Anspruch 2, worin der Keimbildungsbeschleuniger durch die Formel
    Figure imgb0189
     dargestellt ist.
  13. Verfahren nach Anspruch 2, worin der Keimbildungsbeschleuniger durch die Formel
    Figure imgb0190
     dargestellt ist, worin Z1, Z2 und Z3 jeweils (A1)̵pA2-B oder ein Halogenatom, eine Alkoxygruppe mit 1 bis 20 Kohlenstoffatomen, eine Hydroxygruppe, eine Hydroxyaminogruppe oder eine substituierte oder nicht-substituierte Aminogruppe bedeuten, mit der Maßgabe, daß wenigstens eines von Z1, Z2 und Z3 (A1)̵pA2-B ist.
  14. Verfahren nach Anspruch 1, worin das Hydrazinderivat durch die Formel R21-NHNH-CHO dargestellt ist, worin R21 eine aliphatische Gruppe mit 1 bis 30 Kohlenstoffatomen oder eine aromatische Gruppe, umfassend eine monocyclische oder dicyclische Arylgruppe, ungesättigte heterocyclische Gruppe oder das Kondensationsprodukt der ungesättigten heterocyclischen Gruppe mit der monocyclischen oder dicyclischen Arylgruppe, ist.
  15. Verfahren nach Anspruch 1, worin der Keimbildungsbeschleuniger der Formel (Ia) in einer Menge von 5 mg/m2 bis 500 mg/m2 zu dem photographischen Material zugegeben wird.
  16. Verfahren nach Anspruch 1, worin der Keimbildungsbeschleuniger der Formel (Ib) in einer Menge von 1 mg/m2 bis 250 mg/m2 zu dem photographischen Material zugegeben wird.
  17. Verfahren nach Anspruch 1, worin das Hydrazinderivat in einer Menge von 1 mg/m2 bis 300 mg/m2 zugegeben wird.
  18. Verfahren nach Anspruch 1, worin der Entwickler Sulfitionen mit einer Konzentration von wenigstens 0,15 Mol/l enthält.
EP89100317A 1988-01-11 1989-01-10 Verfahren zur Erzeugung von extrem hochkontrastreichen negativen Bildern Expired - Lifetime EP0324426B1 (de)

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US5200298A (en) * 1989-05-10 1993-04-06 Fuji Photo Film Co., Ltd. Method of forming images
DE4310327A1 (de) 1993-03-30 1994-10-06 Du Pont Deutschland Verfahren zur Erzeugung von Negativbildern mit ultrasteilem Kontrast
DE4311888A1 (de) * 1993-04-10 1994-10-13 Du Pont Deutschland Lichtempfindliches Silberhalogenid-Aufzeichnungsmaterial mit verminderter Druckempfindlichkeit
JP3238005B2 (ja) * 1994-06-24 2001-12-10 三菱製紙株式会社 ハロゲン化銀写真感光材料
JP2002351002A (ja) * 2001-05-25 2002-12-04 Fuji Photo Film Co Ltd 画像形成方法
DOP2006000010A (es) 2005-01-10 2006-07-31 Arena Pharm Inc Procedimiento para preparar eteres aromáticos
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EP3242666A1 (de) 2015-01-06 2017-11-15 Arena Pharmaceuticals, Inc. Verfahren zur behandlung von erkrankungen im zusammenhang mit dem s1p1-rezeptor
JP6838744B2 (ja) 2015-06-22 2021-03-03 アリーナ ファーマシューティカルズ， インコーポレイテッド Ｓ１Ｐ１レセプター関連障害における使用のための（Ｒ）−２−（７−（４−シクロペンチル−３−（トリフルオロメチル）ベンジルオキシ）−１，２，３，４−テトラヒドロシクロペンタ［ｂ］インドール−３−イル）酢酸（化合物１）の結晶性Ｌ−アルギニン塩

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US8933083B2 (en) 2003-01-14 2015-01-13 Arena Pharmaceuticals, Inc. 1,2,3-trisubstituted aryl and heteroaryl derivatives as modulators of metabolism and the prophylaxis and treatment of disorders related thereto such as diabetes and hyperglycemia
US8546429B2 (en) 2003-07-11 2013-10-01 Arena Pharmaceuticals, Inc. 1,2,3-trisubstituted aryl and heteroaryl derivatives as modulators of metabolism and the prophylaxis and treatment of disorders related thereto

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