WO2004077152A1 - Materiau photosensible aux couleurs a base d'halogenure d'argent - Google Patents

Materiau photosensible aux couleurs a base d'halogenure d'argent Download PDF

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Publication number
WO2004077152A1
WO2004077152A1 PCT/JP2003/002022 JP0302022W WO2004077152A1 WO 2004077152 A1 WO2004077152 A1 WO 2004077152A1 JP 0302022 W JP0302022 W JP 0302022W WO 2004077152 A1 WO2004077152 A1 WO 2004077152A1
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WO
WIPO (PCT)
Prior art keywords
layer
silver halide
sensitive
sensitivity
silver
Prior art date
Application number
PCT/JP2003/002022
Other languages
English (en)
Japanese (ja)
Inventor
Hiroshi Inoie
Original Assignee
Konica Corporation
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 Konica Corporation filed Critical Konica Corporation
Priority to PCT/JP2003/002022 priority Critical patent/WO2004077152A1/fr
Publication of WO2004077152A1 publication Critical patent/WO2004077152A1/fr

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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • G03C2007/3034—Unit layer
    • 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
    • G03C2200/00—Details
    • G03C2200/27—Gelatine content
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material), and more particularly to a silver halide color photographic light-sensitive material having improved sensitivity and graininess.
  • magenta coupler in terms of shelf life, even if the expiration date is exceeded, the magenta coupler will be damaged by toxic gases such as formaldehyde, causing it to become a so-called magenta fading negative, and prints that have turned green None endless.
  • toxic gases such as formaldehyde
  • the green photosensitive layer has a silver / gelatin coating amount ratio (mass ratio) of at least 0.4 and at most 0.6, inclusive of a 2-equivalent anilinopyrazo-magenta coupler.
  • Silver strength photo-sensitive material represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent.
  • R 2 represents an aryl group.
  • 3 represents a substituent and ni represents 1 to Represents an integer of 5. When ni is 2 or more, R 3 may be the same or different.
  • the green light-sensitive layer is a layer containing a green light-sensitive silver halide emulsion having the highest sensitivity, and then a layer containing a green light-sensitive silver halide emulsion having the highest sensitivity.
  • the silver halide color photographic light-sensitive material according to (1) is a layer containing a green light-sensitive silver halide emulsion having the highest sensitivity, and then a layer containing a green light-sensitive silver halide emulsion having the highest sensitivity.
  • the magenta turbidity represented by the general formula (1) contained in the green photosensitive layer is 65 mol% or more of all couplers contained in the green photosensitive layer.
  • the present invention provides a silver halide color photographic light-sensitive material having at least two adjacent green light-sensitive layers on a support, wherein at least two of the green light-sensitive layers are represented by the general formula (1).
  • the green photosensitive layer has a silver-no-gelatin coating amount ratio (mass ratio) of 0.4 or more and 0.6 or less.
  • the green light-sensitive layer is a layer containing a green light-sensitive silver halide emulsion having the highest sensitivity, and then a layer containing a green light-sensitive silver halide emulsion having the highest sensitivity.
  • the magenta coupler represented by the general formula (1) is 65 mol% or more of all couplers contained in the green photosensitive layer.
  • the coupler represented by the general formula (1) represents a hydrogen atom or a group which can be removed by a reaction with an oxidized form of an aromatic primary amine color developing agent.
  • R represents a substituted thioallyl group, Particularly, a thiophenyl group having a diffusion preventing group is preferable.
  • R 2 represents an aryl group, preferably a phenyl group substituted with a group such as halogen, alkoxy, cyano, substituted sulfone, and acylamino.
  • R 3 represents a substituent, and examples thereof include groups such as acylamino, sulfone, sulfamoyl, sulfonamide, and carboalkoxy.
  • n represents an integer of 1 to 5. When n is 2 or more, R 3 may be the same or different.
  • couplers can be used together with magenta couplers other than the present invention, they are preferably used in a range of 65 mol% to 85 mol% of all magenta couplers in the same layer, and more preferably. It is used in the range of 70 mol% or more and 80 mol% or less.
  • the coupler of the present invention may be used alone, or two or more of the couplers of the present invention may be used in combination.
  • the green light-sensitive silver halide emulsion layer may be a two-layer unit composed of a high-sensitivity layer and a low-sensitivity layer, or a high-sensitivity layer.
  • a three-layer unit consisting of a sensitivity layer and a low-sensitivity layer, and a multi-layer unit of more layers can be used.
  • a multilayer unit having three or more layers a case in which it is used for all green-sensitive layers is also a preferable embodiment.
  • the compound represented by the general formula (1) can be synthesized by an ordinary method well known to those skilled in the art.
  • Gelatin is used as the hydrophilic colloid used in the green light-sensitive silver halide emulsion layer according to the present invention, and lime-processed gelatin, acid-processed gelatin, and Bu 11 1.Soc.Sci. Photon. Japan, No. 16, page 30 (1966), as well as gelatin derivatives (e.g., acid halides, acid anhydrides, isocyanates, etc.) , Bromoacetic acid, alkansaltones, vinylsulfonamides, maleimide compounds, polyalkylenoxides, epoxy compounds, etc.).
  • gelatin derivatives e.g., acid halides, acid anhydrides, isocyanates, etc.
  • the coating ratio (mass ratio) of AgZ gelatin in the green photosensitive layer according to the present invention is set in the range of 0.4 or more and 0.6 or less.
  • the inventor of the present invention has found that when using the magenta razor brush represented by the general formula (1), to improve sensitivity and granularity, Ag / gelatin It has been found that setting the coating amount ratio appropriately is most effective, and the present invention has been accomplished.
  • the coating amount ratio of Ag / gelatin in the layer containing the green light-sensitive silver halide emulsion having the highest sensitivity and then in the layer containing the green light-sensitive silver halide emulsion having the highest sensitivity By appropriately setting the coating amount ratio of Ag / gelatin in the layer containing the green light-sensitive silver halide emulsion having the highest sensitivity and then in the layer containing the green light-sensitive silver halide emulsion having the highest sensitivity, The effect of the present invention is exhibited, and if only one side is used, the sensitivity of the adjacent layer is reduced, which is not preferable. If only one side is set, the oxidized amount of the color developing agent, which is the reaction product of the exposed silver halide emulsion and the color developing agent, is reduced, and as a result, the development balance is changed. It is assumed that a drop occurs.
  • the silver halide photographic light-sensitive material according to the present invention comprises, in addition to the green-sensitive silver halide emulsion layer, at least one red-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer. It consists of a silver emulsion layer and a non-photosensitive layer.Each photosensitive silver halide emulsion layer may be a two-layer unit consisting of a high-sensitivity layer and a low-sensitivity layer, or a high-sensitivity layer, if necessary. Alternatively, it may be a three-layer unit composed of a medium sensitivity layer and a low sensitivity layer.
  • non-photosensitive layer for example, an antihalation layer, a yellow filter layer, an intermediate layer, or a protective layer (outermost layer) can be provided.
  • an antihalation layer for example, a yellow filter layer, an intermediate layer, or a protective layer (outermost layer)
  • a protective layer outermost layer
  • Halogen composition is not uniform 9 9 3 I-I B
  • UV absorber 10 0 3 VIII-I
  • Couplers can be used in the photosensitive layer according to the present invention, and specific examples thereof are described in RD. The relevant sections are described below.
  • Soluble coupler 100 1 VII- — Section E
  • Each of the above additives can be added by a dispersion method described in RD308119 XIV or the like.
  • the silver halide photographic light-sensitive material according to the present invention may be provided with an auxiliary layer such as a single filter or an intermediate layer described in the aforementioned RD 3081, 19VII-K.
  • the silver halide photographic light-sensitive material according to the present invention can have various layer constitutions such as a forward layer, an inverse layer, and a unity constitution described in the aforementioned RD 3081, 19VII-K.
  • TH Geormes Theory of Photographic Process, 4th Edition, 291-334 And a known developer described in Journal of the American Chemical Society, Vol. 73, No. 3, page 100 (1951). can do. Further, development can be carried out by a conventional method described in RD 17643, pages 28 to 29, RD 18716, page 615 and RD 308 119 XIX.
  • Samples of silver halide color photographic material were prepared by sequentially forming each layer having the composition shown below from the support side on a 125 ⁇ m-thick triacetyl cell orifice film support provided with an undercoat layer. was prepared.
  • the amount of each material added below are expressed in grams per 1 m 2. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.
  • Silver iodobromide emulsion d 0.10
  • Silver iodobromide emulsion g 0.38
  • each silver iodobromide emulsion used in the preparation of Sample 101 is shown in the table below.
  • the average grain size of silver iodobromide emulsions c, d, e, f, g, and h is the diameter (average value) of a circle having the same projected area (average value). i is represented by the length of one side of the cube (average value).
  • Silver iodobromide emulsion Average grain size Average iodine content Average aspect ratio ( ⁇ ) (mol%) (Average grain size / thickness)
  • Silver iodobromide emulsion c 0, 6 1 3.1 5.43 Silver iodobromide emulsion d 0.98 3. 7 6.10 Silver iodobromide emulsion e 0.95 8.0 0.37 Silver iodobromide Emulsion ⁇ 1.43 3.9 6.76 Silver iodobromide emulsion g 1.50 3.16.60 Silver iodobromide emulsion h 1.23 7.9 2.85 Silver iodobromide emulsion i 0.043 1.9-After adding each sensitizing dye as described above, each emulsion was added with sodium thiosulfate, chloroauric acid, potassium thiocyanate, etc., and subjected to chemical sensitization to optimize the relationship of the Kabbly sensitivity. did.
  • the specific photographic sensitivity was 200 as a result of measurement according to the method specified in Japanese Industrial Standard JIS K76 14-1981, which was established in accordance with the international standard IS0 sensitivity.
  • Sample 101 In the preparation of Sample 101 above, the silver-gelatin coating amount ratio of each of the low-, medium-, and high-sensitivity green light-sensitive layers of the seventh, eighth, and ninth layers was unchanged. Samples 102 to 110 were prepared in the same manner except that the amount of gelatin was adjusted and changed as shown in the table below.
  • magenta density characteristic curve of the photographic D-L 0 g E characteristic curve created above the reciprocal of the exposure required to obtain a density of +0.10 from the minimum density is defined as sensitivity, and the sample 101 The relative sensitivity with the sensitivity being 1.00 was determined.
  • the magenta density of the RMS value (capri density +0.30 (condition 3) and +0.70 (condition b)) was measured using the aperture scanning area.
  • the change in density value (1000 times as large as the change in density value caused by scanning through a green filter with a 250 ⁇ m 2 microdensitometer) was measured.
  • the granularity is expressed as a relative value with the RMS value of sample 101 set to 1.00, and the smaller the value, the better the granularity.
  • the sample of the present invention is superior in sensitivity and granularity to the comparative example, especially the layer having the highest sensitivity and the second highest sensitivity.
  • Samples in which the AgZ gelatin ratio of the layer is in the range of 0.40 to 0.60 show that the graininess is remarkably improved.
  • Sample 101 of Example 1 the coating amount ratio of silver Z gelatin in each of the low-, medium-, and high-sensitivity green photosensitive layers of the seventh, eighth, and ninth layers was changed by changing the amount of silver.
  • Sample 20 was prepared in the same manner except that the amount of gelatin was adjusted and changed as shown in the table below. 1 to 205 were prepared.
  • Example 1 the type of magenta turbidity (denoted as M-Cp. In the table) contained in the high-sensitivity green photosensitive layer and the middle-sensitivity green photosensitive layer, and included in the layers
  • samples 301 to 309 shown in the following table were produced based on the sample 201 of Example 2.
  • the AgZ gelatin ratio of the high-sensitivity layer and the medium-sensitivity layer of Samples 301 to 308 was the same as that of Sample 201, and was added to each layer of Samples 301 to 309.
  • the total amount of the M coupler and the CM coupler was the same as that of Sample 101.
  • the constitution specified in the present invention can provide a silver halide silver halide photographic light-sensitive material having high sensitivity and excellent graininess.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

L'invention concerne un matériau photosensible aux couleurs à base d'halogénure d'argent à sensibilité et granularité améliorées. Ledit matériau photosensible aux couleurs à base d'halogénure d'argent comprend un support et au moins deux couches adjacentes sensibles au vert disposées sur ledit support. Ce matériau est caractérisé en ce que les couches adjacentes sensibles au vert contiennent un copulant magenta équivalent à deux anilinopyrazolones représenté par la formule (1), et en ce que les couches sensibles au vert présentent un rapport argent/gélatine (en poids) compris entre 0,4 et 0,6.
PCT/JP2003/002022 2003-02-25 2003-02-25 Materiau photosensible aux couleurs a base d'halogenure d'argent WO2004077152A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2003/002022 WO2004077152A1 (fr) 2003-02-25 2003-02-25 Materiau photosensible aux couleurs a base d'halogenure d'argent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2003/002022 WO2004077152A1 (fr) 2003-02-25 2003-02-25 Materiau photosensible aux couleurs a base d'halogenure d'argent

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002174875A (ja) * 2000-12-06 2002-06-21 Konica Corp ハロゲン化銀写真感光材料
JP2002207268A (ja) * 2001-01-11 2002-07-26 Konica Corp ハロゲン化銀写真感光材料及びその処理方法
JP2002221775A (ja) * 2001-01-24 2002-08-09 Konica Corp ハロゲン化銀カラー写真感光材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002174875A (ja) * 2000-12-06 2002-06-21 Konica Corp ハロゲン化銀写真感光材料
JP2002207268A (ja) * 2001-01-11 2002-07-26 Konica Corp ハロゲン化銀写真感光材料及びその処理方法
JP2002221775A (ja) * 2001-01-24 2002-08-09 Konica Corp ハロゲン化銀カラー写真感光材料

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