US3804633A - Light-sensitive silver halide photographic material - Google Patents

Light-sensitive silver halide photographic material Download PDF

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Publication number
US3804633A
US3804633A US00177185A US17718571A US3804633A US 3804633 A US3804633 A US 3804633A US 00177185 A US00177185 A US 00177185A US 17718571 A US17718571 A US 17718571A US 3804633 A US3804633 A US 3804633A
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US
United States
Prior art keywords
photographic material
light
silver halide
copolymer
emulsion
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
US00177185A
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English (en)
Inventor
K Sakamoto
I Fushiki
F Shimizu
K Tozawa
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.)
Konica Minolta Inc
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Konica Minolta Inc
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.)
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Publication of US3804633A publication Critical patent/US3804633A/en
Assigned to KONICA CORPORATION reassignment KONICA CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: KONISAIROKU PHOTO INDUSTRY CO., LTD.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • ABSTRACT Graininess of a light-sensitive silver halide photographic material is improved by incorporating in any of the layers thereof a copolymer containing a nvinylpyrrolidone unit with a mercaptotetrazole compound of the general formula,
  • R R and R are individually a hydrogen atom, an alkyl, alkenyl or alkynyl group, or an aryl or aralkyl group, and R and R, may be same or differem.
  • This invention relates to a light-sensitive silver halide photographic material improved in grainless of an image obtained by the development thereof.
  • the former method has such drawbacks that the expensive silver halide is required in large quantities, so that the photographic material becomes high in cost and, at the same time, the formation of fog becomes easy, while the latter method has such drawbacks that the effect of the chemical incorporated varies depending on the kind of coupler used, so that the coupler to be used in combination therewith is limited, or there is brought about marked desensitization.
  • the present invention provides a lightsensitive silver halide photographic material excellent in graininess which has been prepared by use of a silver halide photographic material incorporated with the combination of (I a poly-N-vinylpyrrolidone or a copolymer containing a N-vinylpyrrolidone unit and (11 a compound (hereinafter referred to as mercaptotetrazole compound") of the general formula (II),
  • copolymer (l).-l8 N-Vinylpyrmlidone/morpholino- 20:20:60
  • copolymer (ID-28 CHa5 n as Among the high polymers used in the present invention, all the copolymers containing vinylpyrrolidone can display marked graininess-improving effects when used in combination with the mercaptotetrazole compounds, though the degrees of said effects vary depending on the monomer ratios. nab If necessary, the above-mentioned high polymers and (HH; mercaptotetrazole compounds may individually be Q- CH1 used in the form of mixtures of two or more.
  • the high polymer and mercapto compound may be incorporated into one emulsion layer, and may be incorporated not only into emulsion layers adjacent to each other but 11 -11 alsointo such auxiliary layer as sub layer, inter layer or -0CH a protective layer. These compounds may be incorporated into a silver halide emulsion at any step during the preparation of the silver halide emulsion, but it is w more effective to incorporate the compounds during the second ripening, or prior to coating, of the silver halide emulsion.
  • the temperature and time of the second rip- (IDM ening should be selected properly, whereby excellent photographic properties can be imparted to the resulting light-sensitive photographic material.
  • the compounds may be incorpo- (HHS 0,11, rated into the coupler dispersion.
  • CHICHICHIN The amounts of the compounds to be incorporated 01H yary depending on the kinds of said compounds, but it 15 particularly effective to incorporate the high polymer D- in an amount of 0.2- to 100 g., and the mercaptotet- CH,OH: H:CH: aN razole compound in an amount of 0.001 to 10 g., per
  • the high polymer is desirably one which is soluble in water or alkali. If the high polymer is not soluble in said liquid, it is dissolved in a solvent such as methanol, ethanol, acetone, ethyl acetate, dioxane, di-
  • the mercaptotet- Compound R: R: razole compound may also be dissolved in the same (19.20 .41 manner as in the case of the high polymer, and the resulting solution is added to a silver halide emulsion or (ID-22 Q auxiliary layer-forming liquid.
  • the photographic emulsions used in the present in- CD43 3 vention include emulsions of AgCl, AgBr, AgClBr, Ag-
  • emulsions may have been optically sensitized with cyanine and merocyanine compounds, and may have been subjected to chemical sensitization treatments using sulfur-containing compounds, noble metal salts, polyalkylene oxide derivatives or reducing H 0 H3 0 compounds.
  • couplers applicable tothe case of light-sensitive color photographic materials there may be used those which can produce a color image by means of p-phenylenediamine type color developers. Examples of these couplers are yellow cou plers having benzoyl acetanilide groups, magenta couplers having a pyrazolone or indazolone nucleus or a cyanoacetyl group'and cyan couplers having a phenol or naphthol nucleus.
  • couplers may contain in the active methyleneor methine-portions a substituent capable of releasing by color development reaction such as, for example, halogens, or arylazo, aryloxy or arylthio groups. Further, these couplers may contain in the molecule either one or both of a non-diffusible group such as, for example, a long chain alkyl group or an alkylphenoxy group, and a water-solubilizing group such as, for example, a sulfonic group or a carboxyl group.
  • a non-diffusible group such as, for example, a long chain alkyl group or an alkylphenoxy group
  • a water-solubilizing group such as, for example, a sulfonic group or a carboxyl group.
  • those which are oleophilic are dissolved in a high boiling organic solvent, e.g.
  • the light sensitive layer may be composed of protective layer, yellow layer, yellow filter layer, magenta layer, inter layer, cyan layer, antihalation layer and support in this order from the upper-most layer, or may be composed of magenta, cyan and yellow layers in this order, though the order varies depending on the intended application of the photographic material.
  • the color developing layer may be composed of one or 2 layers.
  • the support for use in the present invention there is ordinarily used a paper or a natural or synthetic high polymer films of the cellulose acetate or polyester type.
  • the thus obtained light-sensitive photographic material according to the present invention is a blackwhite photographic material
  • it may be developed by treatment with a solution containing Metol, hydroquinone and phenidone
  • the photographic material is a color photographic material
  • it may be developed by using a color developer of the pphenylenediamine type to form a color image directly by the first development, as in the case of a color negative, or it may be subjected to black-white development using Metol and hydroquinone and then to treatment for forming a color image, like the reversal color treatment.
  • Typical examples of the black-white developing agent used for development of the light-sensitive photographic material according to the present invention are hydroquinone, p-phenylenediamine, paminophenol, Metol, pyrogallol, amidol, glycine and l-phenyl-3-pyrazolidone.
  • Typical examples of the color developing agent are sulfates, chlorides and sulfites of N,N-diethyl-pphenylenediamine, N-ethyl-N- hydroxyethyl-p-phenylenediamine, N-ethyl-N- hydroxyethyl-p-phenylenediamine, N-ethyl-N- hydroxyethyl-Z-methyI p-phenylenediamine and N ethyl-N-B-methanesulfonamidoethyl-3-methyl-4- aminoanil ine,
  • the present invention is applicable also to mixed packet type light-sensitive color photographic materials and DTR method light-sensitive materials.
  • EXAMPLE 1 A high speed light-sensitive gelatinous silver iodobromide emulsion containing 3.5 mole percent of Agl and g. of gelatin per mole of AgX was subjected to second ripening, and incorporated with 0.18 g. per mole of AgX of a spectral sensitizing dye of the structure,
  • Coupler l Coupler (2)
  • composition of the coupler dispersion was as shown below in which the amount of each constituent is per mole of AgX.
  • Coupler (1 16 g. Coupler (2) 4 g. 2,5-Di-(t)-octyl hydroquinone 0.5 g. Tricresyl phosphate 20 g. Ethyl acetate 30 g. 5% Alkanol B (trade mark of Du Pom.) 15 ml. 3% Gelatin 400 ml.
  • the relative speed, fog and RMS graininess at the point of color image density value of 0.3 in the developed photographic materials were as set forth in Table l.
  • the RMS graininess referred to herein is a value of 1,000 times the standard deviation of variations in density value observed when a sample, which has been exposed and developed under definite conditions, is scanned by means of a microdensitometer having circular scanning openings of 2.5 p. in diameter.
  • EXAMPLE 2 The red-sensitive emulsion used in Example 1 was mixed with a coupler dispersion of the composition shown below. The amount of each constituent of the coupler dispersion was per mole of AgX.
  • Composition of Composition of coupler coupler dispersion dispersion Coupler (2) 45 g. 45 g. Tricresyl phosphate 30 g. 30 g. Ethyl acetate 50 g. 50 g. Compound (ll)-l0 0.3 g. 3% Gelatin 300 ml. 300 ml. 5% Alkanol B 50 ml. 50 mlv High polymer (1)-5 10 g.
  • EXAMPLE 3 Each of the two light-sensitive photographic materials prepared in Example (2) was exposed to a definite light and then subjected to reversal treatment using Kodak Process E IV-Kit (Trademark of Eastman Kodak Co.).
  • EXAMPLE 4 A highspeed light-sensitive gelatinous silver lOdObI'CF: mide photographic emulsion containing 5.0 mole percent of Ag], and 120 g. of gelatin per mole of AgX was subjected to second ripening, and incorporated with 0.20 g. per mole of AgX of a spectral sensitizing dye of the structure shownbelow and 1.8 g. per mole of AgX of 5-methyl-7-hydroxy-l ,3,4-triazaindolizine to prepare a panchromatic emulsion.
  • Spectral sensitizing dye :
  • This emulsion was incorporated with the high polymer (l)-] 6 and the mercaptotetrazole compound (ll)-9 in such a combination as shown in Table 4. To the emulsion were then added, per mole of AgX, 100 ml. of 1 percent formalin and 200 ml. of5 percent saponin. Subsequently, the emulsion was coated on a cellulose triacetate film base to a dry film thickness of 4 u and then dried to prepare a photographic material. This photographic material was exposed through an optical wedge to a definite light and then subjected to the following black-white development treatment:
  • EXAMPLE 6 A high speed light-sensitive gelatinous silver iodobromide photographic emulsion containing 4.5 mole percent of AgI, and g. of gelatin per mole of AgX was subjected to second ripening, and incorporated with 0.1 3 g. per mole of AgX of a spectral sensitizing dye of the structure shown below and 1.4 g. per mole of AgX of 5-methyl-7-hydroxy-l,3,4-triazaindolizine to prepare a green-sensitive photographic emulsion.
  • Spectral sensitizing dye Spectral sensitizing dye:
  • This emulsion was incorporated with a high polymer and a mercaptotetrazole compound in such a combination as shown in Table 6. Thereafter, a coupler (4) of the structure shown below was subjected to a high speed rotary mixer to form a dispersion.
  • Coupler (4)
  • the composition of the coupler dispersion was as shown below in which the amount of each constituent is per mole of AgX.
  • Coupler (4) Tricresyl phosphate Ethyl acetate 5% Alkanol B 3% Gelatin g. 20 g. 250 g. 120 ml.
  • the above-mentioned coupler dispersion was mixed with the aforesaid emulsion to which were then added, per mole of AgX, 90 ml. of 1 percent formalin and 300 ml. of 5 percent saponin. Subsequently, the emulsion was coated on a cellulose triacetate film base to a dry film thickness of 5 p. and then dried to prepare a lightsensitive photoggphic material. This photograph ic ma terial was subjected to the same development treatment as in Example 1 to obtain the results set forth in Table 6.
  • R R and R are individually a hydrogen atom, an alkyl, alkenyl or alkynyl group, or an aryl or aralkyl group, and R and R may be same or different and wherein the N-vinyl-pyrrolidone polymer or copolymer is used in an amount of 0.2 g. to 100 g. per mole of silver halide contained therein and the mercaptotetrazole compound is used in an amount of 0.001 g. to 10 g. per mole of silver halide which material comprises a binder consisting essentially of gelatin and the polymer or copolymer of N-vinylpyrrolidone.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US00177185A 1970-09-04 1971-09-01 Light-sensitive silver halide photographic material Expired - Lifetime US3804633A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45077072A JPS4913566B1 (enrdf_load_stackoverflow) 1970-09-04 1970-09-04

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US3804633A true US3804633A (en) 1974-04-16

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JP (1) JPS4913566B1 (enrdf_load_stackoverflow)
DE (1) DE2144314A1 (enrdf_load_stackoverflow)
GB (1) GB1337667A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4232118A (en) * 1978-03-10 1980-11-04 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
US4281059A (en) * 1978-12-12 1981-07-28 Konishiroku Photo Industry Co., Ltd. Photographic material
EP0440947A3 (en) * 1990-02-01 1993-02-17 Minnesota Mining And Manufacturing Company Infrared sensitive silver halide photographic elements

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3252801A (en) * 1961-07-10 1966-05-24 Du Pont Photographic emulsions, layers and elements
US3266897A (en) * 1964-03-02 1966-08-16 Eastman Kodak Co Antifoggant agents for photography
US3615617A (en) * 1968-12-03 1971-10-26 Agfa Gevaert Ag Stabilized photographic material with tetrazole thiocarbonic acid ester

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3252801A (en) * 1961-07-10 1966-05-24 Du Pont Photographic emulsions, layers and elements
US3266897A (en) * 1964-03-02 1966-08-16 Eastman Kodak Co Antifoggant agents for photography
US3615617A (en) * 1968-12-03 1971-10-26 Agfa Gevaert Ag Stabilized photographic material with tetrazole thiocarbonic acid ester

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4232118A (en) * 1978-03-10 1980-11-04 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
US4281059A (en) * 1978-12-12 1981-07-28 Konishiroku Photo Industry Co., Ltd. Photographic material
EP0440947A3 (en) * 1990-02-01 1993-02-17 Minnesota Mining And Manufacturing Company Infrared sensitive silver halide photographic elements
US5543278A (en) * 1990-02-01 1996-08-06 Minnesota Mining And Manufacturing Company Infrared sensitive silver halide photographic elements

Also Published As

Publication number Publication date
DE2144314A1 (de) 1972-07-27
JPS4913566B1 (enrdf_load_stackoverflow) 1974-04-01
GB1337667A (en) 1973-11-21

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Owner name: KONICA CORPORATION, JAPAN

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:KONISAIROKU PHOTO INDUSTRY CO., LTD.;REEL/FRAME:005159/0302

Effective date: 19871021