US3320068A - Silver halide emulsions with increased sensitivity - Google Patents

Silver halide emulsions with increased sensitivity Download PDF

Info

Publication number
US3320068A
US3320068A US356075A US35607564A US3320068A US 3320068 A US3320068 A US 3320068A US 356075 A US356075 A US 356075A US 35607564 A US35607564 A US 35607564A US 3320068 A US3320068 A US 3320068A
Authority
US
United States
Prior art keywords
gold
emulsion
added
sample
solution
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
US356075A
Other languages
English (en)
Inventor
Muller-Bardorff Wolfgang
Saleck Wilhelm
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.)
Agfa Gevaert NV
Original Assignee
Agfa AG
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 Agfa AG filed Critical Agfa AG
Application granted granted Critical
Publication of US3320068A publication Critical patent/US3320068A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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

Definitions

  • Numerous compounds are known which can be used as additives to the emulsion or developer to increase the sensitivity of a photographic layer. Many different terms are used for substances that have this effect, e.g., chemical sensi-tizers or activators.
  • the best known class of substances in this field are polyalkylene oxides, in particular polyethylene oxides and water-soluble onium compounds such as quaternary ammonium-, phosphoniumand sulphonium salts or combinations thereof or derivatives of thiourea, for example, thiouronium salts.
  • the most commonly used combination for gold sensitization consists of gold-(III)-salts and thiocyanate or thiosulphate, although the solutions of thiocyanate are not very stable and those of thiosulphate are diflicult to pre pare.
  • Reaction kinetic investigations e.g., by Protass, Bjirrum and Kirschner (Z. Wiss. Angew. Phot. Kine l, 455 (1956)) on gold complexes with thiocyanate ions admit of the assumption that sensitization is caused by a controlled, slow decomposition of the Au-(I)-complexes in which the thiocyanate ions participate.
  • the mecha nism of this sensitization process is not certain since many reaction components are involved, such as metallic gold, Au-(I)-, Au-(IID- and thiocyanate ions, dithiocyanogen and additional sulphur degradation products including thiosulphate and gelatine.
  • R represents a hydrogen atom or an alkyl group preferably lower alkyl up to 5 carbon atoms, which may be substituted, for example, with hydroxyl, halogen such as C1 or Br, carboxyl, or an aryl group preferably phenyl which may be substituted, for example with alkyl, preferably lower alkoxy, halogen preferably C1 or Br, carboxyl, amine, hydroxyl, x represents a hydrogen atom, a hydroxyl group or a halogen atom preferably chlorine and bromine;
  • the phenolic benzene ring in the above general formula can in addition be substituted, especially in the o-position or p-position to the hydroxy group, with lower alkyl radicals preferably those having up to 3 carbon atoms which may be substituted if desired, or with halogen atoms preferably chlorine and bromine, hydroxy or lower alkoxy groups preferably those having up to 3 carbon atoms.
  • CHz-OHr-OH CHrN CH2OOOH CHz-COOH uch compounds are already known. They can be easily reduced by reacting the appropriate substituted salicylldehyde with the appropriate amine.
  • the resulting chiffs bases are hydrogenated in aqueous solution with 1e aid of a Raney nickel catalyst.
  • the substituent R can 1en be introduced with the aid of active chlorine comounds in an aqueous alkaline medium.
  • the bromine can be subseuently introduced.
  • These o-hydroxybenzylamin-compounds are good comlexing agents for heavy and noble metal ions.
  • gold-(III)-chloride gold-(III)-cornplexes are ormed, which are often deep in color. Due to the weakly :ducing effect of the compounds of the above general ormula, such Au-(III) complexes are reduced to Au-(I) omplexes. To ensure the formation of the Au-(l)-comlexes in every case, it is advisable to additionally add 168k reducing agents.
  • the process of the invention is capable of being used Ilih all photographic silver halide emulsions.
  • the silver alide can consist of silver chloride, silver bromide, silver )dide or mixtures thereof.
  • the emulsions can be further sensitized with, for xample, sulphur compounds, polyalkylene oxides, wateroluble onium compounds or combinations of polyethylne oxides and onium compounds.
  • they can e optically sensitized by, e.g., cyanine or merocyanine lyestuffs and the like.
  • Basic stabilizers can be included in the emulsions, for xample, organic mercapto compounds, quaternary benzhiazoles, triazoles, tetrazaindolizines and the like.
  • ome of the compounds according to the invention proluce the same sensitivity with half the quantity of gold, usually with less fogging.
  • the mode of addition of the o-hydroxybenzylamin- :om pounds of the invention to the emulsions is not critical.
  • Fhe compounds may be added in dissolved or in solid orrn, and before, during or after the addition of the noble netal salt.
  • the noble metal salt for exlmple, gold-(IID-chloride, may be first mixed with a .olution of the o hydroxybenzylamin-compounds and then ldded to the emulsions.
  • this addiion is made before the chemical ripening of the emul- .ion.
  • the chemical ripening is also called after-ripening.
  • lhe compounds are used in concentrations of 0.1 g. to i g.
  • emulsion per kg. of emulsion (preferably 0.25-0.35 g./kg.).
  • optimum quantity to be added depends on the reiucing power of the o-hydroxybenzylamin-compound and he nature of the emulsion. It can easily be determined Jy a few tests.
  • the o-hydroxybenzylamin-compounds are used in :ombination with weak reducing agents.
  • Suitable for this purpose are, for example, the polyhydroxycarboxylic acids, in particular those of the following general formula:
  • n is 0 or an integer between 1 and 8, advantageously l5, e.g., hydroxyacetic acid, d-gluco-ot-hexonic acid, d-gluco-a-heptonic acid, etc.
  • Suitable are also aldo sugars, such as glucose, dimethylformamide, nitrilotriacetic acid and similar compounds.
  • aldo sugars such as glucose, dimethylformamide, nitrilotriacetic acid and similar compounds.
  • suitable for the present purpose are those reducing agents which are able to reduce trivalent gold to monovalent gold, but have too small a reduction potential to precipitate metallic gold from the complexes of the monovalent gold.
  • the process can be varied in many ways even when using the o-hydroxybenzyl-amin-compounds in combination with the previously described weak reducing agents.
  • the compounds can be added, in dissolved or in solid form, before, during or after the addition of the noble metal salt.
  • the noble metal salt for example, gold-(IlD-chloride
  • gold-(IlD-chloride) can first of all have added thereto a solution of the compounds according to the invention, be thereafter reduced with'the reducing agent and then the gold-(I)-complex solution can be added to the emulsions.
  • the addition compounds are generally added prior to the chemical or after-ripening of the emulsion.
  • the compounds are used in concentrations from 0.1 g. to 5 g. preferably 0.25-0.35 g. per kg.
  • emulsion with addition of 0.1 to 5 g. preferably 0.l50.3 g. of the reducing agent.
  • the optimum quantity of the reducing agent depends on the reducing power of the compounds and the nature of the emulsion, and can easily be determined by a few tests.
  • the reducing agents should generally be used in a concentration which is smaller than or at most equal to that of the o-hydroxy-benzylarnine derivatives.
  • the amount to be used can be between 0.1 g./kg. of emulsion and the amount of the o-hydroxybenzylamine complexing agent.
  • Example 1 A highly sensitive gelatino-silver bromiodide emulsion with a 4 mol percent of silver iodide, which contains 50 g. of silver per liter, has 35-40 mg./ liter of KBr and sulphurcompounds, etc. added thereto for the chemical ripening in the usual way and is divided before the ripening into three samples A, B and C.
  • Sample A serves as standard sample. Before the ripening, the following solution is added to sample B, per lite-r of emulsion:
  • the three samples are exposed and developed in a normal commercial p-methylaminophenol hydroquinone de veloper for 10 minutes at 20 C.
  • Example 2 A highly sensitive silver bromoiodide emulsion, as described in Example 1, is pretreated as in this example and divided into three samples A, B and C.
  • Sample A serves as standard sample.
  • Sample B has added thereto, per liter of emulsion, a mixture consisting of 3 ml. of a aqueous solution of the Compound III and 1 ml. of 0.08% gold-(III)-chloride solution.
  • Sample C contains, per liter of emulsion, 3 ml. of a 10% aqueous solution of the Compound III, which has been mixed with 2 ml. of a 0.08% gold-(III)-chloride solution.
  • Example 1 The three samples are ripened as in Example 1, then coated as described therein onto a film support, and then the material is exposed and developed as described in Example 1.
  • Sample A serves as standard sample.
  • Sample B has added thereto, per liter of emulsion, a mixture of 3 ml. of a 10% aqueous solution of Compound II and 1 ml. of a 0.08% gold-(III)-chloride solution.
  • Sample C contains, per liter of emulsion, 3 ml. of a 10% aqueous solution of Compound II, which has been mixed with 2 ml. of a 0.08% gold-(III)-chloride solution.
  • Example 1 The ripening of the three samples, the casting onto a film support, the exposure and the development is performed as indicated in Example 1.
  • Sample A without additives serves as standard sample.
  • Sample B has added thereto, per liter of emulsion, a mixture of 3 ml. of a 10% aqueous solution of the Compound VIII, and 1 ml. of a 0.08% gold-(HD-chloride solution.
  • Sample C contains, per liter of emulsion, 3 ml. of a 10% aqueous solution of the Compound VIII, which has been mixed with 2 ml. of a 0.08% gold-(IID-chloride solution.
  • Example 5 A highly sensitive gelatino-silver bromiodide emulsion with 4 mol percent of silver iodide, which contains 50 g. of silver per liter, has 35-40 mg./lit'er of KBr and sulphur compounds etc. for the chemical ripening, is divided before ripening into 3 samples A, B and C.
  • Sample A serves as comparison sample. Before the ripening of sample B, the latter has added thereto the following solution, per liter of emulsion:
  • a wetting agent and a stabilizer e.g., of the azaindolizine type are added to each of the three samples which are then cast onto a support such as paper, a cellulose acetate, a polyester preferably of polyethylene terephthalate or a polycarbonate in particular of bis-hydroxyphenyl alkanes.
  • the three samples are exposed and developed in a commercial p-methylaminophenyl hydroquinone developer for 10 minutes at 20 C.
  • Example 6 Three samples A, B and C of a silver halide emulsion, as described in Example 5, are treated as follows:
  • Sample A serves as standard sample. Before being chemically ripened, Sample B has the following solution added thereto, per liter of emulsion:
  • Sample C has added thereto, per liter of emulsion, a
  • Sample A serves as standard sample. Before being hemically ripened, Sample B has the following solution dded thereto, per liter of emulsion:
  • Sample C has added thereto, per liter of emulsion, a mixture which has been prepared as follows:
  • Sample A is a standard sample. Before the after-ripenng of Sample B the following solution is added per liter )f emulsion:
  • a wetting agent and a stabilizer e.g., of the azaindolizine type, is added thereto. Thereafter the emulsions are coated onto a usual support. The two samples are exposed and developed for minutes at 20 C. in an X-ray developer which yields silver images with a steep characteristic curve.
  • Example 10 A gelatino-silver bromoiodide emulsion of medium sensitivity with 6 mol. percent of silver iodide, which contains g. of silver per liter and which further contains potassium bromide and sulphur compounds, etc, for the chemical ripening is divided before after-ripening into two samples A and B.
  • Sample A is the standard sample.
  • a wetting agent and a stabilizer e.g., of the azaindolizine type, are added and they are then cast onto a usual support.
  • the two samples are exposed and developed for 10 minutes at 20 C. in a p-methylaminophenol hydroquinone developer.
  • a gelatino-silver chlorobromoiodide emulsion with 20 mol percent of silver chloride and 6 mol percent of silver iodide which contains g. of silver per liter and which further contains potassium bromide and sulphur compounds etc. for the chemical ripening is divided before after-ripening into :two samples A and B.
  • Sample A is the comparison sample.
  • the samples are after-ripened up to maximum sensitivity, thereafter a wetting agent and a stabilizer, e.g., of the azaindolizine type, are added and the samples are cast onto a paper support.
  • a wetting agent and a stabilizer e.g., of the azaindolizine type
  • the noble metal salts are not limited to the previously mentioned, because it is possible to use any suitable salt which is soluble in water or lower alcohols.
  • suitable salt which is soluble in water or lower alcohols.
  • Such compounds are: gold halides, such as auric chloride, or complex gold halides, such as potassium chloroaurate (KAuCh) and sodium .chloroaurate (NaAuCl
  • gold compounds, such as auric sulfate are practically as useful as the gold halides. Aurous, as well as auric compounds can be used.
  • Complex gold salts such as alkali metal aurous thiosulfates, alkali metal aurous sulfites (e.g., sodium or potassium aurous thiosulfate and sodium or potassium aurous sulfite).
  • alkali metal aurous thiosulfates e.g., sodium or potassium aurous thiosulfate and sodium or potassium aurous sulfite.
  • Potassium chloroaurite, potassium bromoaurite, potassium iodoaurite, or the corresponding sodium, calcium, strontium, cadmium or gallium salts can also be used.
  • Suitable salts of noble metals of the VIII group are ammonium or potassium, cbloropalladate, ammonium, sodium and potassium chloroplatinate, ammonium potassium and sodium bromoplatinate, ammonium chlororhodate, ammonium chlororuthenate, ammonium chloroiridate, ammonium, potassium and sodium chloroplatinite, ammonium, potassium and sodium chloropalladite, etc.
  • the after-ripening of the emulsion with the noble metal salt and the o-hydroxybenzylamine compounds is performed at an appropriate temperature particularly between 30 and 60 C.
  • the pH of the emulsion is advantageously adjusted to the acid side of neutrality preferably between 5 and 7. Maintenance of the emulsion on the acid side of neutrality during coating of the emulsion is also preferred.
  • the noble metal salts are employed in an amount below that which produces a substantial fog.
  • a quantity of the noble metal salt is employed, equivalent to between 0.1 and mg. of the noble metal per :mole of silver halide in the emulsion.
  • the noble metal compounds are preferably incorporated in the emulsion in the form of their solutions in a suitable sol-vent such as water, methyl alcohol, ethyl alcohol or the like.
  • a process for producing a sensitized photographic silver halide emulsion the step which comprises afterripening the emulsion on the acid side of neutrality in the effective presence of at least one water-soluble salt of a Group VIII metal having an atomic weight of greater than or gold and in the effective presence of an o-hydroxybenzylamine compound of the formula wherein R represents a substitutent of the group consisting of hydrogen, al-kyl, and a phenyl, x stands for a member of the group consisting of hydrogen, hydroxy and halogen and n in an integer between 1 and 5.
  • the emulsion which is to be after-ripened additionally contains at least one member of the group consisting of sulfur compounds, onium compounds, polyalkylene oxides and a tetraazainclolizine stabilizer.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US356075A 1963-04-24 1964-03-31 Silver halide emulsions with increased sensitivity Expired - Lifetime US3320068A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA42947A DE1174156B (de) 1963-04-24 1963-04-24 Verfahren zur Steigerung der Empfindlichkeit von Halogensilberemulsionen unter Verwendung von Edelmetallsalzen

Publications (1)

Publication Number Publication Date
US3320068A true US3320068A (en) 1967-05-16

Family

ID=6933390

Family Applications (1)

Application Number Title Priority Date Filing Date
US356075A Expired - Lifetime US3320068A (en) 1963-04-24 1964-03-31 Silver halide emulsions with increased sensitivity

Country Status (5)

Country Link
US (1) US3320068A (en:Method)
BE (1) BE647035A (en:Method)
CH (1) CH440961A (en:Method)
DE (1) DE1174156B (en:Method)
GB (1) GB1033255A (en:Method)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4943628A (en:Method) * 1972-08-31 1974-04-24
DE2508137A1 (de) * 1974-02-25 1975-09-04 Fuji Photo Film Co Ltd Verfahren zur herstellung von lithographischem lichtempfindlichem material
US3915713A (en) * 1972-11-02 1975-10-28 Fuji Photo Film Co Ltd Silver halide photographic emulsion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4943628A (en:Method) * 1972-08-31 1974-04-24
US3901711A (en) * 1972-08-31 1975-08-26 Mitsubishi Paper Mills Ltd Silver halide photographic emulsion containing a gold salt and a polyalkylene oxide
US3915713A (en) * 1972-11-02 1975-10-28 Fuji Photo Film Co Ltd Silver halide photographic emulsion
DE2508137A1 (de) * 1974-02-25 1975-09-04 Fuji Photo Film Co Ltd Verfahren zur herstellung von lithographischem lichtempfindlichem material

Also Published As

Publication number Publication date
GB1033255A (en) 1966-06-22
CH440961A (de) 1967-07-31
BE647035A (en:Method) 1964-10-26
DE1174156B (de) 1964-07-16

Similar Documents

Publication Publication Date Title
US3503749A (en) Light-sensitive silver halide emulsions containing soluble gold salts
US2448060A (en) Photographic emulsions sensitized with salts of metals of group viii of the periodicarrangement of the elements
US3531289A (en) Silver halide photographic emulsions improved by new precipitation methods
US2598079A (en) High-speed photographic silver halide emulsions supersensitized with palladium salts
US3650749A (en) Photographic development
US3519426A (en) Preparation of silver halide emulsions having high covering power
US3615617A (en) Stabilized photographic material with tetrazole thiocarbonic acid ester
US4054457A (en) Silver halide emulsions containing hexathiocane thiones as sensitizers
US3320068A (en) Silver halide emulsions with increased sensitivity
EP0339870A1 (en) Novel antifoggant for polyalkylene glycol sensitizers
US3645738A (en) Stabilizing silver image in presence of heterocyclic thioxo compound containing sulphogroup
US4423140A (en) Silver halide emulsions containing aromatic latent image stabilizing compounds
US5328820A (en) Silver halide photographic emulsions sensitized in the presence of organic disulfides and sulfinates
JPS6122293B2 (en:Method)
US3650759A (en) Silver halide emulsion containing 1.2-glycol as sensitizer and antifoggant
US3554758A (en) Photographic light-sensitive material
US3556797A (en) Cobalt (ii) and manganese (ii) chelates as photographic emulsion antifoggants
US3326690A (en) Silver halide emulsions with increased sensitivity
US4065312A (en) Process for the production of photographic vesicular images in photographic silver halide material
US3396022A (en) Quinone stabilizers and antifoggants for silver halide emulsions
JPH07199390A (ja) 写真要素及び写真方法
US3615490A (en) Photographic overcoat comprising a benzotriazole toning agent and a silver salt of 5-mercapto-1-substituted tetrazole
US2713541A (en) Stabilized photographic silver halide emulsions
US3318702A (en) Silver halide emulsions with increased sensitivity
EP0068997A1 (en) Photographic silver halide element containing an antistain agent or antistain agent precursor