WO2004012011A1 - Silver halide color-photographic sensitive material for photography - Google Patents

Silver halide color-photographic sensitive material for photography Download PDF

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Publication number
WO2004012011A1
WO2004012011A1 PCT/JP2002/007524 JP0207524W WO2004012011A1 WO 2004012011 A1 WO2004012011 A1 WO 2004012011A1 JP 0207524 W JP0207524 W JP 0207524W WO 2004012011 A1 WO2004012011 A1 WO 2004012011A1
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WO
WIPO (PCT)
Prior art keywords
silver halide
value
sensitive
layer
silver
Prior art date
Application number
PCT/JP2002/007524
Other languages
French (fr)
Japanese (ja)
Inventor
Masaru Iwagaki
Original Assignee
Konica Minolta Photo Imaging, 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.)
Filing date
Publication date
Application filed by Konica Minolta Photo Imaging, Inc. filed Critical Konica Minolta Photo Imaging, Inc.
Priority to CNA028293584A priority Critical patent/CN1639635A/en
Priority to PCT/JP2002/007524 priority patent/WO2004012011A1/en
Publication of WO2004012011A1 publication Critical patent/WO2004012011A1/en

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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
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density
    • 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
    • G03C1/0051—Tabular grain emulsions
    • 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
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0056—Disclocations
    • 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
    • G03C2200/26—Gamma
    • 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
    • G03C7/3029—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 for photography having excellent gradation characteristics and improved development processing stability.
  • the gradation (also referred to as ⁇ ) of a silver halide color photographic light-sensitive material for photographing is approximately 0.65 for a red-sensitive layer and a green-sensitive layer, and about 0.65 for a blue-sensitive layer. 0.75 is set.
  • color photographic paper is designed according to the gradation of the color negative film described above, and has been widely used as a negative-positive system for general amateurs as a negative-positive system capable of obtaining satisfactory color photographic images on average. are doing.
  • the development processing liquid is replenished with a specified amount of development replenisher corresponding to the processing amount of the photosensitive material, and the activity of the processing liquid is constantly monitored. However, they are adjusted to the standard conditions and managed so that they always fall within the standard conditions.
  • an object of the present invention is to provide a silver halide color photographic light-sensitive material for photographing which can stably obtain a soft gradation even with such fluctuations in the activity of the developing solution.
  • a photographic silver halide for photography having at least two red-sensitive layers, green-sensitive layers, blue-sensitive layers and non-photosensitive layers each having at least two layers having the same color sensitivity and different sensitivities on a support.
  • the ⁇ value in the standard development processing satisfies any of the following conditions, and at least one of the photosensitive layers contains 50% or more of haptic silver halide particles having a total projected area of at least one layer.
  • a photographic silver halide photographic material for photographing comprising a tabular silver halide emulsion having dislocation lines.
  • Red light metering ⁇ value 0.55 to 0.63
  • Green photometry ⁇ value 0.54 to 0.62
  • the y value is defined as the point of minimum density + 0.3 on the characteristic curve consisting of photographic D (density) and Log E (exposure) and 10 times the exposure corresponding to the point. It is defined as the slope (tan 0) of the straight line connecting the density point at the corresponding exposure point.
  • Green light metering ⁇ value 1.1 2 ⁇ : L. 16
  • the red-sensitive layer and the green-sensitive layer are each composed of three layers of a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer, and the density ratio of the maximum density part in the reference development processing. Any one of (1) to (5), wherein the sensitivity layer is within a range of 10 to 20%, the medium sensitivity layer is within a range of 10 to 30%, and the low sensitivity layer is within a range of 50 to 80%.
  • the ⁇ (gamma) value representing the gradient is defined as a minimum density value + 0 on a characteristic curve in which the vertical axis for a photograph is D (density) and the horizontal axis is Log E (exposure amount). .3 is defined as the slope of a straight line connecting the density point at the exposure point corresponding to 10 times the exposure corresponding to the point.
  • the photographic D-Log E characteristic curve shows the density D value of a silver halide color photographic light-sensitive material for photography obtained by exposure and development with a standard white light source at 1.0 minute and the exposure amount E
  • the logarithmic representation of the log E value 1.0 minute is a characteristic curve displayed on a two-dimensional coordinate system displayed on the same scale, and is widely used in the industry.
  • the y value defined above is 0.55 to 0.63 for the red photosensitive layer, 0.54 to 0.62 for the green photosensitive layer, and 0.5. 62 to 0.70, and more preferably of the red-sensitive layer!
  • the value is 0.56 to 0.62
  • the gamma value of the green photosensitive layer is 0.55 to 0.61
  • the gamma value of the blue photosensitive layer is 0.63 to 0.6.
  • each ⁇ value has the following relationship.
  • Red light metering ⁇ value / Green light metering ⁇ value 1.00 to 1.04
  • each of the red light-sensitive layer, the green light-sensitive layer, and the blue light-sensitive layer at least one of a plurality of layers having different sensitivities has 50% or more of the total projected area.
  • 70% or more of the silver halide grains in the total projected area contain a tabular silver halide emulsion having dislocation lines.
  • the dislocation lines referred to in the present invention include, for example, J. F. Hami 1 ton; P hoto. Sci. Eng. 11 (19667) 57, and T. Shiozawa; S ci. P hot o. S ci. Japan 35 (1 97 2) 2 13 page, and can be observed by a direct method using a transmission electron microscope at low temperature. What can be done.
  • the number of dislocation lines is preferably 10 or more, more preferably 20 or more per silver halide grain.
  • the method of introducing dislocation lines For example, a method of adding an aqueous solution of iodide ion such as potassium iodide and a solution of a water-soluble silver salt by double jet, a method of adding fine silver iodide particles, and a method of adding only an iodine ion solution
  • a desired position and amount of dislocation lines can be introduced by a known method such as a method using an iodide ion-releasing compound described in Japanese Patent Application Laid-Open No. 6-11781 / 1994.
  • the position where the dislocation line is formed but it is preferable that the dislocation line is located near the outer periphery, near the ridgeline, or near the vertex of the tabular silver halide grains.
  • the tabular silver halide emulsion has a particle diameter distribution of a circle-converted diameter.
  • the coefficient of variation is 15 to 30%, the effect of the present invention is more exhibited. If the coefficient of variation is too large or too small, the stability of a soft silver halide color photographic light-sensitive material for photographing in the development processing will be reduced.
  • the coefficient of variation of the thickness distribution of the tabular silver halide emulsion is also preferably from 15 to 30%.
  • the above-mentioned variation coefficients of the particle size and thickness are values defined by the following equations.
  • the average particle diameter of the tabular silver halide grains according to the present invention in terms of circle is from 0.2 to; L is preferably 0.1 ⁇ , more preferably 0.3 to 7.0 O zm, and 0.4 to 5 0 ⁇ is most preferred.
  • the thickness is preferably 0.05 to 1.5 ⁇ , more preferably 0.07 to 0.50 ⁇ .
  • the aspect ratio (particle diameter / thickness in terms of circle) is 3 or more, preferably 5 or more, and more preferably 8 or more and 100 or less.
  • the average silver iodide content of the tabular silver halide emulsion contained in the photosensitive layer is 5.0 mol.
  • the silver iodide content and the average silver iodide content of the silver halide emulsion can be determined by using a method (Electron Probe Micro Analyzer). At least 100 silver halide grains By calculating the silver iodide content by the PMA method, the average silver iodide content in the present invention can be obtained from the average of these.
  • the average silver iodide content is measured by other well-known methods such as X-ray fluorescence spectroscopy, ICP (induction plasma) emission spectroscopy, and ICP mass spectrometry. It can also be determined by measuring the content.
  • the total coated silver amount is preferably 3.0 OgZm 2 or more and 4.0 g / m 2 or less. More preferably, it is not less than 3.1 g / m 2 and not more than 3.9 g / m 2 .
  • the effect of the present invention can be further enhanced by controlling the total silver coating amount of the silver halide color photographic light-sensitive material for photography to the range specified above.
  • the total coated silver referred to in the present invention includes photosensitive silver halide, non-photosensitive silver halide, and colloidal silver, each of which is represented by a value converted to metallic silver.
  • the total amount of silver coated silver halide color photographic light-sensitive material used be as small as possible.However, if it is easily reduced, not only will the image quality deteriorate, However, the density stability during development may be degraded.
  • the stability in the developing process can be enhanced even with a small amount of silver.
  • One of the features of the present invention is that it contains a tabular silver halide emulsion having the above-mentioned dislocation lines, and as a result, the total dry film thickness of the photographic constituent layers is 1%.
  • the red light-sensitive layer and the green light-sensitive layer are each composed of three layers of a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer having the same color sensitivity and different sensitivities, and are subjected to the standard development processing.
  • the concentration ratio of the maximum density part is 10 to 20%, 10 to 30 ° / 0 , 50 to 8 °%, preferably 12 to 20%, 15 to By being within the range of 30% and 50 to 73%, the effect of the present invention is more exhibited. That is, even in the case of soft tone, the stability in the development processing can be further enhanced.
  • each coating solution constituting each layer is coated as a single layer on a support with the same coating amount as each layer in a multilayer silver halide color photographic light-sensitive material, and is exposed to light and developed. Can be determined from the maximum concentration of the sample obtained after the above. Both are almost the same.
  • the red, green and blue light-sensitive silver halide emulsion layers of the silver halide color photographic light-sensitive material of the present invention can contain a coupler. It is preferable that the color dye formed from the coupler contained in each of these layers has a spectral absorption maximum separated by at least 20 nm. As the coupler, it is preferable to use a cyan coupler, a magenta coupler, or a yellow coupler.
  • each emulsion layer and a coupler As a combination of each emulsion layer and a coupler, a yellow coupler and a blue-sensitive layer, a magenta coupler and a green-sensitive layer, and a cyan coupler and a red-sensitive layer are usually used. Instead, other combinations may be used.
  • a DIR compound can be used.
  • Specific examples of the DIR compound that can be used include, for example, D-1 to D-34 described in JP-A No. 4-114153, and the present invention preferably uses these compounds.
  • Specific examples of the DIR compound that can be used in the present invention include, in addition to the above, for example, US Pat. Nos. 4,234,678, 3,227,554, 3,647,291, and Nos. 3,958,993, 4,419,886, 3,933,500, JP-A-57-56837, 51-13239, U.S. Pat. No. 363, No. 2, 070, 266 and RD40145, section XIV can be mentioned.
  • Specific examples of the coupler that can be used in the present invention are described in RD40145, section II and the like.
  • the additives used in the present invention can be added by the dispersion method described in RD 40145, Section VIII.
  • the silver halide color photographic light-sensitive material for photography 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 38957, Section XI.
  • the silver halide color photographic light-sensitive material for photography of the present invention can have various layer constitutions such as a forward layer, a reverse layer, and a unit constitution described in Section XI of RD 38957.
  • the silver halide emulsion according to the present invention can be applied to color negative films for general, professional or cinematographic use.
  • the silver halide color photographic light-sensitive material for photography of the present invention can be subjected to development processing other than the standard development processing.
  • development processing other than the standard development processing.
  • Known developers described in the Society Journalofthe American Chemical Society
  • vol. 73, p. 3, 100 (1951) can be used, and the aforementioned RD 38957 can be used.
  • XVII to XX of RD 40145 and XXIII of RD 40145 The development can be performed by the usual method described in the section.
  • a fifth layer (highly sensitive red-sensitive layer) was placed on a 120-m-thick triacetylcellulose film support provided with an undercoat layer.
  • the following emulsion A was used in place of the silver iodobromide emulsion c used in the color layer) and the following emulsion B was used in place of the silver iodobromide emulsion Em-1 used in the ninth layer (highly sensitive green color-sensitive layer).
  • Sample 101 was prepared in the same manner except that the following emulsion C was used instead of the silver iodobromide emulsion g used in the first and second layers (highly sensitive blue-sensitive layer).
  • Sample 10 1 was exposed according to JIS-K-76 14 (1 981). Reference development processing was performed. The transmission Status sM concentration of the sample was measured and a photographic D-LogE characteristic curve was created.
  • red light metering ⁇ value 0.65
  • green light metering ⁇ value 0.64
  • blue light metering ⁇ value 0.73
  • Red photosensitive layer 8 25 5 7%
  • Sample 101 the chemical sensitivity conditions of the silver iodobromide emulsion used in the high-sensitivity layer, the medium-sensitivity layer, and the low-sensitivity layer of each photosensitive layer were determined by the following ⁇ value and ⁇ value balance.
  • Sample 102 was produced by appropriately adjusting the values to be as follows.
  • Sample 102 In the preparation of Sample 102, the following silver iodobromide emulsions D, E, and F were used in place of the silver iodobromide emulsions A, B, and C used in the fifth, ninth, and second layers, respectively.
  • Sample 103 was prepared in the same manner except that was used.
  • Emulsion shape Circle-converted diameter Dislocation line grain size distribution Silver iodide paste ratio number ( ⁇ m) Right ⁇ C, Variation coefficient Content
  • the concentration ratio of the maximum density part of the red photosensitive layer and the green photosensitive layer was the same as that of Sample 103.
  • Sample 105 In the preparation of Sample 104, the following silver iodobromide emulsions G, H, and I were used in place of the silver iodobromide emulsions D, E, and F used in the fifth, ninth, and second layers, respectively. Sample 105 was prepared in the same manner except that was used. Emulsion shape Diameter in circles Dislocation lines Particle size distribution Silver iodide J number ( ⁇ m presence or absence Coefficient of variation Content
  • Sample 105 silver iodobromide emulsions G, H, and I used in the fifth, ninth, and second layers were replaced with the following silver iodobromide emulsions], K, and L, respectively.
  • Sample 106 was prepared in the same manner except that was used.
  • Emulsion shape Diameter in circles Dislocation lines
  • Sample 107 the following silver iodobromide emulsions P, Q, and R were used in place of the silver iodobromide emulsions ⁇ , ⁇ , and ⁇ ⁇ used in the fifth, ninth, and second layers, respectively.
  • a sample 108 was prepared in the same manner except for using.
  • Emulsion shape Circle-converted diameter Dislocation line grain size distribution Silver iodide aspect ratio number ( ⁇ m) C, Coefficient of variation Content
  • Sample 108 In the preparation of Sample 108, the following silver iodobromide emulsions S, T, and U were used in place of the silver iodobromide emulsions P, Q, and R used in the fifth, ninth, and second layers, respectively.
  • a sample 109 was prepared in the same manner except for using.
  • Emulsion shape Circle-converted diameter Diameter curve
  • Green photosensitive layer 8% In preparation of 3260 samples 112 and 113, the preparation conditions were appropriately adjusted so that the ⁇ value and the y value balance were the same as in sample 109.
  • the samples 101 to 113 prepared as described above were evaluated for development processing stability (a), (b), and (c) according to the following method.
  • the development time is +15 seconds, and the same density D e (+15 S) of the processed sample and the development time Measured the same concentration D e ( -15 S) of the treated sample for 15 seconds.
  • the concentration difference (AD G ) was obtained. To the table that the AD G is better smaller.
  • ⁇ ⁇ ⁇ ⁇ round means a point in time when the integrated amount of the replenishment amount of the color developing solution reaches 1Z2 of the processing tank volume of the color developing solution.
  • the green photometric sensitivity was expressed as the reciprocal of the exposure required to obtain a density of minimum density +0.3.
  • the configuration of the present invention has a preferable soft gradation and excellent development processing stability with respect to the activity of the developing solution (development time, continuous processing, and fluctuations in the concentration of the developing agent).
  • a photographic light-sensitive material can be provided.

Abstract

A silver halide color-photographic sensitive material for photography which not only has preferable soft gradation but attains excellent development stability even when the activity of the developing solution changes (factors such as developing time, continuous treatment, and developing agent concentration fluctuate). The photographic sensitive material is characterized in that it comprises a substrate and formed thereon at least two red-sensitive layers, at least two green-sensitive layers, and at least two blue-sensitive layers wherein the layers sensitive to each color are sensitive to the same color and differ in sensitivity, that the photographic sensitive material after standard development has values of Ϝ of 0.55 to 0.63 for red light, 0.54 to 0.62 for green light, and 0.62 to 0.70 for blue light, and that in the layers sensitive to each color, at least one layer contains a platy silver halide emulsion in which at least 50%, in terms of projected area, of all silver halide particles have a dislocation line.

Description

明細書 撮影用ハ口ゲン化銀力ラー写真感光材料 技術分野  Description Silver halide photographic material for photography
本発明は、 階調特性に優れ、 かつ現像処理安定性が改良された撮影用ハロ ゲン化銀カラー写真感光材料に関する。 背景技術  The present invention relates to a silver halide color photographic light-sensitive material for photography having excellent gradation characteristics and improved development processing stability. Background art
撮影用ハロゲン化銀カラー写真感光材料、 いわゆるカラーネガフィルムの 階調度 （γともいう） は、 一般的には、 赤感光性層、 緑感光性層が約 0 . 6 5、 青感光性層が約 0 . 7 5に設定されている。 また、 カラー印画紙は、 上 記のカラーネガフィルムの階調度に合わせて設計されており、 一般アマチュ ァ用としては平均的に満足できる力ラー写真画像が得られるネガ Ζポジシス テムとして、 長年にわたって普及している。  Generally, the gradation (also referred to as γ) of a silver halide color photographic light-sensitive material for photographing, a so-called color negative film, is approximately 0.65 for a red-sensitive layer and a green-sensitive layer, and about 0.65 for a blue-sensitive layer. 0.75 is set. In addition, color photographic paper is designed according to the gradation of the color negative film described above, and has been widely used as a negative-positive system for general amateurs as a negative-positive system capable of obtaining satisfactory color photographic images on average. are doing.
しかしながら、 ポートレート撮影や近年急激に増加しているデジタル画像 処理においては、 その階調度を低くする （軟調にするとも言う） ことによつ て良い階調再現効果が得られる。 特に、 乳幼児の撮影においては、 その肌色 のなめらかさや質感を写真で再現するためには、 階調度の設定が重要な要素 となる。  However, in portrait photography and digital image processing, which has been rapidly increasing in recent years, a good gradation reproduction effect can be obtained by lowering the gradation (also called softening). In particular, when photographing infants, setting the gradient is an important factor in reproducing the smoothness and texture of the skin color in photographs.
しかしながら、 上述の理由により撮影用ハロゲン化銀力ラ一写真感光材料 の階調度を軟調にすると、 現像処理工程で使用する現像処理液の活性度の影 響を受けやすいという欠点がある。 それらは、 階調変動や感度変動として顕 在化してくる。 However, if the gradation of the silver halide photographic light-sensitive material for photographing is softened for the above-mentioned reason, there is a disadvantage that the activity of the developing solution used in the developing process is easily affected. They are manifested as gradation fluctuations and sensitivity fluctuations. Localization.
通常、 現像処理を連続して行う場合には、 現像処理液は感光材料の処理量 に対応して、 規定量の現像補充液が補充され、 また、 処理液の活性度は、 常 時モニターしながら、 基準条件への調整を行い、 常に基準条件内に入るよう 管理がなされている。  Normally, when the development processing is performed continuously, the development processing liquid is replenished with a specified amount of development replenisher corresponding to the processing amount of the photosensitive material, and the activity of the processing liquid is constantly monitored. However, they are adjusted to the standard conditions and managed so that they always fall within the standard conditions.
現像処理液の管理が厳重に行われていれば問題はないが、 単位時間あたり の現像処理量が少ない場合、 あるいは連続的に処理がなされずに、 間欠的に 処理を行う場合、あるいは現像処理が停止した、例えば、休日等をはさんで、 現像を再開するような場合には、 現像処理液の活性度にわずかな変動がおき る場合がある。  There is no problem if the development processing liquid is strictly controlled, but if the amount of development processing per unit time is small, or if processing is performed intermittently without continuous processing, or When the development has been stopped, for example, when the development is restarted after a holiday, etc., the activity of the developing solution may fluctuate slightly.
したがって、 本発明の目的は、 このような現像処理液の活性度の変動があ つても、 安定して軟調な階調度が得られる撮影用ハロゲン化銀カラー写真感 光材料を提供することである。 発明の開示  Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material for photographing which can stably obtain a soft gradation even with such fluctuations in the activity of the developing solution. . Disclosure of the invention
本発明の上記目的は、 下記の各々の構成により達成される。  The above object of the present invention is achieved by each of the following constitutions.
( 1 ) 支持体上にそれぞれ同一感色性で感度の異なる少なくとも 2層から なる赤感光性層、 緑感光性層、 青感光性層と非感光性層とを有する撮影用ハ 口ゲン化銀カラー写真感光材料において、 基準現像処理での γ値が下記のい ずれの条件も満たし、 かつ各感光性層の少なくとも 1層が、 全投影面積の 5 0 %以上のハ口ゲン化銀粒子が転位線を有する平板状ハ口ゲン化銀乳剤を含 有することを特徴とする撮影用ハ口ゲン化銀力ラ一写真感光材料。  (1) A photographic silver halide for photography having at least two red-sensitive layers, green-sensitive layers, blue-sensitive layers and non-photosensitive layers each having at least two layers having the same color sensitivity and different sensitivities on a support. In a color photographic light-sensitive material, the γ value in the standard development processing satisfies any of the following conditions, and at least one of the photosensitive layers contains 50% or more of haptic silver halide particles having a total projected area of at least one layer. A photographic silver halide photographic material for photographing, comprising a tabular silver halide emulsion having dislocation lines.
赤光測光 γ値 = 0 . 5 5〜 0 . 6 3 緑光測光 γ値 =0. 54〜0. 62 Red light metering γ value = 0.55 to 0.63 Green photometry γ value = 0.54 to 0.62
青光測光 γ値 =0. 6 2〜0. 70  Blue light metering γ value = 0.6 2 to 0.70
ただし y値とは、 写真用 D (濃度） 一 L o g E (露光量） からなる特性曲 線上において、 最小濃度値 + 0. 3の点と、 該点に対応する露光量の 10倍 量に対応する露光量点における濃度点とを結ぶ直線の傾き （t a n 0) と定 義する。  However, the y value is defined as the point of minimum density + 0.3 on the characteristic curve consisting of photographic D (density) and Log E (exposure) and 10 times the exposure corresponding to the point. It is defined as the slope (tan 0) of the straight line connecting the density point at the corresponding exposure point.
(2) 前記各 γ値が、下記のいずれの条件も満たすことを特徴とする （1) に記載の撮影用ハ口ゲン化銀力ラ一写真感光材料。  (2) The photographic material according to (1), wherein each of the γ values satisfies any of the following conditions:
赤光測光 γ値ノ緑光測光 γ値 = 1. 00〜1. 04  Red light metering γ value Green light metering γ value = 1.00 to 1.04
青光測光 γ値ノ緑光測光 γ値 = 1. 1 2〜： L. 1 6  Blue light metering γ value Green light metering γ value = 1.1 2 ~: L. 16
(3) 前記平板状ハロゲン化銀乳剤が、 円換算直径の粒径分布の変動係数 が 1 5〜30%であることを特徴とする （1) 又は （2) に記載の撮影用ハ 口ゲン化銀力ラ一写真感光材料。  (3) The photographic hagen according to (1) or (2), wherein the tabular silver halide emulsion has a variation coefficient of a particle diameter distribution of a circle-equivalent diameter of 15 to 30%. Silver halide photo-sensitive material.
(4) 前記平板状ハロゲン化銀乳剤が、 平均沃化銀含有率が 5. 0モル％ 以下であることを特徴とする （1) 〜 （3) のいずれか 1項に記載の撮影用 ハ口ゲン化銀力ラー写真感光材料。  (4) The photographic film according to any one of (1) to (3), wherein the tabular silver halide emulsion has an average silver iodide content of 5.0 mol% or less. Silver sensitized silver photographic material.
(5) 総塗布銀量が、 3. O g/m2以上、 4. O g/m2以下であること を特徴とする （1) 〜 （4) のいずれか 1項に記載の撮影用ハロゲン化銀力 ラー写真感光材料。 (5) The photographing method according to any one of (1) to (4), wherein the total applied silver amount is 3.O g / m 2 or more and 4.O g / m 2 or less. Silver halide color photographic material.
(6) 前記赤感光性層と緑感光性層とが、 それぞれ高感度層、 中感度層、 及び低感度層の 3層からなり、 かつ基準現像処理での最大濃度部の濃度割合 ヽ 該高感度層が 1 0〜20%、 該中感度層が 1 0〜30%、 該低感度層が 50〜 80 %の範囲内にあることを特徴とする （1) 〜 （5) のいずれか 1 項に記載の撮影用ハ口ゲン化銀力ラ一写真感光材枓。 発明を実施するための最良の形態 (6) The red-sensitive layer and the green-sensitive layer are each composed of three layers of a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer, and the density ratio of the maximum density part in the reference development processing. Any one of (1) to (5), wherein the sensitivity layer is within a range of 10 to 20%, the medium sensitivity layer is within a range of 10 to 30%, and the low sensitivity layer is within a range of 50 to 80%. The silver halide silver halide photo-sensitive material for photography according to the above item. BEST MODE FOR CARRYING OUT THE INVENTION
本発明において、階調度を表す γ (ガンマ）値とは、 写真用の縦軸が D (濃 度）、 横軸が L o g E (露光量） からなる特性曲線上において、最小濃度値 + 0. 3の点と、 該点に対応する露光量の 1 0倍量に対応する露光量点におけ る濃度点とを結ぶ直線の傾きと定義する。  In the present invention, the γ (gamma) value representing the gradient is defined as a minimum density value + 0 on a characteristic curve in which the vertical axis for a photograph is D (density) and the horizontal axis is Log E (exposure amount). .3 is defined as the slope of a straight line connecting the density point at the exposure point corresponding to 10 times the exposure corresponding to the point.
写真用 D— L o g E特性曲線は、 標準白色光源によって露光され、 現像処 理されて得られた撮影用ハロゲン化銀カラー写真感光材料の濃度 D値の 1. 0分と、 露光量 Eの対数表示 L o g E値の 1. 0分が同じスケールで表示さ れる 2次元座標系に表示された特性曲線を意味し、 業界において広く使用さ れている。  The photographic D-Log E characteristic curve shows the density D value of a silver halide color photographic light-sensitive material for photography obtained by exposure and development with a standard white light source at 1.0 minute and the exposure amount E The logarithmic representation of the log E value 1.0 minute is a characteristic curve displayed on a two-dimensional coordinate system displayed on the same scale, and is widely used in the industry.
本発明においては、上記で定義された y値が、赤感光性層が 0. 5 5〜0. 6 3、 緑感光性層が 0. 54〜 0. 6 2、 青感光性層が 0. 6 2〜 0. 70 であり、 さらに好ましくは、 赤感光性層の！値が 0. 5 6〜0. 6 2、 緑感 光性層の γ値が 0. 5 5〜 0. 6 1、 青感光性層の γ値が 0. 6 3〜0. 6 In the present invention, the y value defined above is 0.55 to 0.63 for the red photosensitive layer, 0.54 to 0.62 for the green photosensitive layer, and 0.5. 62 to 0.70, and more preferably of the red-sensitive layer! The value is 0.56 to 0.62, the gamma value of the green photosensitive layer is 0.55 to 0.61, and the gamma value of the blue photosensitive layer is 0.63 to 0.6.
9である。 9
また、本発明においては、各 γ値が以下の関係にあることが特に好ましく、 下記条件を共に満足することにより、 軟調であっても忠実ですぐれた色再現 性を実現することができる。  In the present invention, it is particularly preferable that each γ value has the following relationship. By satisfying both of the following conditions, faithful and excellent color reproducibility can be realized even in a soft tone.
赤光測光 γ値/緑光測光 γ値 = 1. 00〜1. 04  Red light metering γ value / Green light metering γ value = 1.00 to 1.04
青光測光 γ値/緑光測光 γ値 = 1. 1 2〜1. 1 6  Blue light metering γ value / Green light metering γ value = 1.12 to 1.16
本発明の γ値を測定するための基準現像処理は、 ァニュアル .ォブ .ザ - プリティッシュ · ジャーナノレ ·ォブ ' フォトグラフィー （An n u a l o f t h e B r i t i s h J o u r n a l o f P h o t o g r a p h y ) P 1 96〜： L 98 ( 1 9 8 8) に示されるカラーネガフィルム用の処 理工程及び処理液により行うものとする。 The standard development processing for measuring the γ value of the present invention is performed by manual (Principle of the Journal of British Journal of Photography) P196-: The processing steps and processing solutions for color negative films shown in L98 (1989). I do.
本発明においては、 赤感光性層、 緑感光性層、 青感光性層の各感光性層に おいて、 感度の異なる複数の層の少なくとも 1層が、 全投影面積の 5 0%以 上、 好ましくは全投影面積の 70 %以上のハロゲン化銀粒子が転位線を有す る平板状ハ口ゲン化銀乳剤を含有することを特徴とする。  In the present invention, in each of the red light-sensitive layer, the green light-sensitive layer, and the blue light-sensitive layer, at least one of a plurality of layers having different sensitivities has 50% or more of the total projected area. Preferably, 70% or more of the silver halide grains in the total projected area contain a tabular silver halide emulsion having dislocation lines.
本発明でいう転位線とは、 例えば、 J . F. H a m i 1 t o n ; P h o t o . S c i . E n g. 1 1 ( 1 9 6 7) 5 7頁や、 T. S h i o z a w a ； J . S o c . P h o t o. S c i . J a p a n 3 5 (1 9 7 2) 2 1 3頁に 記載されており、 低温での透過型電子顕微鏡を用いた直接的な方法で観察す ることができるものをいう。  The dislocation lines referred to in the present invention include, for example, J. F. Hami 1 ton; P hoto. Sci. Eng. 11 (19667) 57, and T. Shiozawa; S ci. P hot o. S ci. Japan 35 (1 97 2) 2 13 page, and can be observed by a direct method using a transmission electron microscope at low temperature. What can be done.
転位線は、 ハロゲン化銀 1粒子あたり 1 0本以上、 さらには 20本以上有 することが好ましい。 転位線の導入方法に関しては特に限定はなく、 例えば 沃化カリゥムのような沃素イオン水溶液と水溶性銀塩溶液をダブルジエツト で添加する方法、 沃化銀微粒子を添加する方法、 沃素イオン溶液のみを添加 する方法、 特開平 6— 1 1 78 1号等に記載の沃素イオン放出化合物を用い る方法等の公知の方法により、 所望の位置及び量の転位線を導入することが できる。 転位線を形成させる位置について特別な限定はないが、 平板状ハロ ゲン化銀粒子の外周部近傍や稜線近傍、 又は頂点近傍に存在することが好ま しい。  The number of dislocation lines is preferably 10 or more, more preferably 20 or more per silver halide grain. There is no particular limitation on the method of introducing dislocation lines.For example, a method of adding an aqueous solution of iodide ion such as potassium iodide and a solution of a water-soluble silver salt by double jet, a method of adding fine silver iodide particles, and a method of adding only an iodine ion solution A desired position and amount of dislocation lines can be introduced by a known method such as a method using an iodide ion-releasing compound described in Japanese Patent Application Laid-Open No. 6-11781 / 1994. There is no particular limitation on the position where the dislocation line is formed, but it is preferable that the dislocation line is located near the outer periphery, near the ridgeline, or near the vertex of the tabular silver halide grains.
本発明においては、 平板状ハロゲン化銀乳剤が、 円換算直径の粒径分布の 変動係数が 1 5〜30%であることによって、 本発明の効果がより発揮され る。 変動係数が大きすぎても、 小さすぎても、 軟調な撮影用ハロゲン化銀力 ラー写真感光材料の現像処理での安定性が低下してしまう。 平板状ハロゲン 化銀乳剤の厚さ分布の変動係数も、 1 5〜30%であることが好ましい。 上述の粒径や厚さの変動係数は、 下式によって定義される値である。 In the present invention, the tabular silver halide emulsion has a particle diameter distribution of a circle-converted diameter. When the coefficient of variation is 15 to 30%, the effect of the present invention is more exhibited. If the coefficient of variation is too large or too small, the stability of a soft silver halide color photographic light-sensitive material for photographing in the development processing will be reduced. The coefficient of variation of the thickness distribution of the tabular silver halide emulsion is also preferably from 15 to 30%. The above-mentioned variation coefficients of the particle size and thickness are values defined by the following equations.
粒径の変動係数 （％) = (粒径の標準偏差/ /粒径の平均値） X 1 00 厚さの変動係数 （％) = (厚みの標準偏差ノ粒径の平均値） X I 00 ただし、 上記の各測定値は、 平板状ハロゲン化銀粒子を任意に 500個以上 測定して得られた値から求めるものとする。  Coefficient of variation of grain size (%) = (standard deviation of grain size // average of grain size) X 100 Variation coefficient of thickness (%) = (average value of grain size of standard deviation of thickness) XI 00 Each of the above measured values is determined from values obtained by arbitrarily measuring 500 or more tabular silver halide grains.
本発明に係る平板状ハロゲン化銀粒子の円換算直径の平均粒径は、 0. 2 〜； L 0. Ο μπιが好ましく、 0. 3〜7. O zmがより好ましく、 0. 4〜 5. 0 μηιが最も好ましい。 厚さは、 0. 05〜1. 5 μπιが好ましく、 更 に好ましくは 0. 07〜0. 50 μΐηである。 アスペク ト比 （円換算直径の 粒径/厚さ） は 3以上、 好ましくは 5以上、 さらに好ましくは 8以上 1 00 以下である。  The average particle diameter of the tabular silver halide grains according to the present invention in terms of circle is from 0.2 to; L is preferably 0.1 μππ, more preferably 0.3 to 7.0 O zm, and 0.4 to 5 0 μηι is most preferred. The thickness is preferably 0.05 to 1.5 μπι, more preferably 0.07 to 0.50 μη. The aspect ratio (particle diameter / thickness in terms of circle) is 3 or more, preferably 5 or more, and more preferably 8 or more and 100 or less.
本発明においては、 感光性層に含有される平板状ハロゲン化銀乳剤の平均 沃化銀含有率が 5. 0モル。 /0以下であることが好ましく、 より好ましくは 0 . 50モル0 /0以上、 4. 5モル0 /0以下、特に好ましくは 1. 0モル％以上 4. 0モル。 /0以下である。 平板状ハロゲン化銀乳剤を上記構成とすることにより 、 本発明の効果がより発揮される。 In the present invention, the average silver iodide content of the tabular silver halide emulsion contained in the photosensitive layer is 5.0 mol. Preferably / 0 or less, more preferably 0. 50 mol 0/0 or more, 4.5 mol 0/0 or less, particularly preferably 1.0 mol% or more 4.0 mol. / 0 or less. When the tabular silver halide emulsion has the above structure, the effects of the present invention can be further exhibited.
ハロゲン化銀乳剤の沃化銀含有率及び平均沃化銀含有率は、 ΕΡΜΑ法 （ E l e c t r o n P r o b e M i c r o An a l y z e r、法） を用レヽ ることにより求めることができる。 少なくとも 100個のハロゲン化銀粒子 について E PMA法により沃化銀含有率を求めれば、 これらの平均から本発 明でいう平均沃化銀含有率が求められる。 また、 平均沃化銀含有率の測定は 蛍光 X線分析法、 I CP (誘導プラズマ） 発光分析法、 I CP質量分析法な ど、 よく知られた他の方法で、 乳剤全体の沃化銀含有率を測定することによ つても求めることができる。 The silver iodide content and the average silver iodide content of the silver halide emulsion can be determined by using a method (Electron Probe Micro Analyzer). At least 100 silver halide grains By calculating the silver iodide content by the PMA method, the average silver iodide content in the present invention can be obtained from the average of these. The average silver iodide content is measured by other well-known methods such as X-ray fluorescence spectroscopy, ICP (induction plasma) emission spectroscopy, and ICP mass spectrometry. It can also be determined by measuring the content.
本発明の撮影用ハロゲン化銀カラー写真感光材料では、 総塗布銀量が 3. O gZm2以上、 4. 0 g/m2以下であることが好ましい。 更に好ましくは 3. 1 g/m2以上、 3. 9 g/m2以下である。 撮影用ハロゲン化銀カラー 写真感光材料の総塗布銀量を、 上記で規定する範囲とすることにより、 本発 明の効果がより発揮される。 なお、 本発明でいう総塗布銀の中には、 感光性 ハロゲン化銀、 非感光性ハロゲン化銀、 コロイド銀が含まれ、 それぞれ金属 銀に換算した値で示される。 In the silver halide color photographic light-sensitive material for photography of the present invention, the total coated silver amount is preferably 3.0 OgZm 2 or more and 4.0 g / m 2 or less. More preferably, it is not less than 3.1 g / m 2 and not more than 3.9 g / m 2 . The effect of the present invention can be further enhanced by controlling the total silver coating amount of the silver halide color photographic light-sensitive material for photography to the range specified above. The total coated silver referred to in the present invention includes photosensitive silver halide, non-photosensitive silver halide, and colloidal silver, each of which is represented by a value converted to metallic silver.
撮影用ハロゲン化銀カラー写真感光材料の総塗布銀量は、 省資源の観点か ら銀の使用量はできる限り少なくすることが求められているが、 安易に低減 すると画質が劣化するだけでなく、 現像処理での濃度安定性が劣化すること がある。  From the viewpoint of resource saving, it is required that the total amount of silver coated silver halide color photographic light-sensitive material used be as small as possible.However, if it is easily reduced, not only will the image quality deteriorate, However, the density stability during development may be degraded.
本発明の構成では、 軟調な階調であっても、 転位線を有する平板状ハロゲ ン化銀乳剤と組み合わせることにより、 低銀量でも現像処理での安定性を高 めることができる。  In the constitution of the present invention, even in the case of a soft gradation, by combining with a tabular silver halide emulsion having dislocation lines, the stability in the developing process can be enhanced even with a small amount of silver.
本発明においては、 上記転位線を有する平板状ハロゲン化銀乳剤を含有す ることが特徴のひとつであり、 その結果、 写真構成層の乾燥膜厚の総和を 1 One of the features of the present invention is that it contains a tabular silver halide emulsion having the above-mentioned dislocation lines, and as a result, the total dry film thickness of the photographic constituent layers is 1%.
2 μ m〜 20 μ m、 より好ましくは 1 3 μ m〜 20 m、 特に好ましくは 12 μm to 20 μm, more preferably 13 μm to 20 m, particularly preferably 1 μm to 20 μm
3 m〜l 9 /xmとすることが可能であり、 本発明の効果をより発揮する上 で好ましい。 、 本発明においては、 赤感光性層と緑感光性層が、 それぞれ同一感色性で感 度の異なる高感度層、 中感度層、 低感度層の 3層からなり、 かつ基準現像処 理での最大濃度部の濃度割合が、 高感度層、 中感度層、 低感度層の順に 10 〜20%、 10〜30°/0、 50〜8◦ %、 好ましくは、 12〜20%、 15 ~30%、 50〜 73%の範囲内であることによって、 本発明の効果がより 発揮される。 すなわち、 軟調であっても現像処理での安定性をより高めるこ とができる。 3 m to l 9 / xm. Is preferred. In the present invention, the red light-sensitive layer and the green light-sensitive layer are each composed of three layers of a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer having the same color sensitivity and different sensitivities, and are subjected to the standard development processing. The concentration ratio of the maximum density part is 10 to 20%, 10 to 30 ° / 0 , 50 to 8 °%, preferably 12 to 20%, 15 to By being within the range of 30% and 50 to 73%, the effect of the present invention is more exhibited. That is, even in the case of soft tone, the stability in the development processing can be further enhanced.
最大濃度部の高感度、 中感度、 低感度各層の濃度割合の測定は、 感光材料 の最大濃度部について、 顕微鏡等を用いてその断層カラー写真を撮影し、 そ れぞれの構成層の濃度測定することによって得られる。 また別の方法として は、 各層を構成する各塗布液を、 多層ハロゲン化銀カラー写真感光材料での 各層と同じ塗布量で、 支持体上に単一層として塗布し、 露光を与えて現像処 理した後に得られる試料の最大濃度から求めることができる。 両者はほぼ一 致する。  To measure the density ratio of each layer of high sensitivity, medium sensitivity and low sensitivity at the maximum density part, take a tomographic color photograph of the maximum density part of the photosensitive material using a microscope etc. and measure the density of each constituent layer. Obtained by measuring. As another method, each coating solution constituting each layer is coated as a single layer on a support with the same coating amount as each layer in a multilayer silver halide color photographic light-sensitive material, and is exposed to light and developed. Can be determined from the maximum concentration of the sample obtained after the above. Both are almost the same.
本発明の撮影用ハロゲン化銀カラー写真感光材料には、 前記以外の公知の ハロゲン化銀乳剤が用いられる。 例えば、 特開昭 6 1 -6643号、 同 61 一 14630号、 同 61— 1 12142号、 同 62— 157024号、 同 6 2— 1 85 56号、 同 63— 92942号、 同 63— 15 16 18号、 同 6 3— 1 63451号、 同 63— 220238号、 同 63— 31 1244号、 リサーチ 'ディスクロージャー （以下、 RDと略す） 38957の I項及び III項、 RD 40145の XV項等を参考にして製造されたものを利用できる。 ハロゲン化銀乳剤は、 物理熟成、 化学熟成及ぴ分光增感を行ったものを使 用することが好ましい。 このような工程で使用される添加剤は、 RD 38 9 57の IV及ぴ V項、 RD 40 145の XV項等に記載されている。 In the silver halide color photographic light-sensitive material for photography of the present invention, known silver halide emulsions other than those described above are used. For example, JP-A-61-6643, JP-A-61-114630, JP-A-61-112142, JP-A-62-157024, JP-A-62-18556, JP-A-63-92942, JP-A-63-1516 No.18, No.63-163431, No.63-220238, No.63-311244, Research 'Disclosure (hereinafter abbreviated as RD) Refer to Sections I and III of 38957, Section XV of RD 40145, etc. Can be used. Use silver halide emulsions that have undergone physical ripening, chemical ripening and spectral sensitization. It is preferred to use Additives used in such a process are described in RD 38 957, Section IV and V, RD 40 145, Section XV, and the like.
本発明に使用できる公知の写真用添加剤は、 同じく RD 38957の 11〜 X項項、 RD40145の I〜ΧΠΙ項に記載のものを用いることができる。 本発明の撮影用ハロゲン化銀カラー写真感光材料の赤、 緑及び青感光性ハ ロゲン化銀乳剤層の各層にカプラーを含有させることができる。 これら各層 に含まれるカプラーから形成される発色色素は、 分光吸収極大が少なくとも 20 nm離れていることが好ましい。 カプラーとしては、 シアンカプラー、 マゼンタカプラー、 イェローカプラーを用いることが好ましい。 各乳剤層と カプラーの組み合わせとしては、 通常、 イェローカプラーと青感光性層、 マ ゼンタカプラーと緑感光性層、 シアンカプラーと赤感光性層の組み合わせが 用いられるが、 これら組み合わせに限られるものではなく、 他の組み合わせ であってもよい。  Known photographic additives that can be used in the present invention include those described in RD 38957, Sections 11 to X and RD40145, Sections I to ΧΠΙ. The red, green and blue light-sensitive silver halide emulsion layers of the silver halide color photographic light-sensitive material of the present invention can contain a coupler. It is preferable that the color dye formed from the coupler contained in each of these layers has a spectral absorption maximum separated by at least 20 nm. As the coupler, it is preferable to use a cyan coupler, a magenta coupler, or a yellow coupler. As a combination of each emulsion layer and a coupler, a yellow coupler and a blue-sensitive layer, a magenta coupler and a green-sensitive layer, and a cyan coupler and a red-sensitive layer are usually used. Instead, other combinations may be used.
本発明においては D I R化合物を用いることができる。 用いることのでき る D I R化合物の具体例としては、 例えば、 特開平 4一 1 14153号に記 載の D— 1〜D— 34が挙げられ、 本発明はこれらの化合物を好ましく用い ることができる。 本発明において用いることのできる D I R化合物の具体例 は、 上記のほかに、 例えば、 米国特許第 4， 234, 678号、 同第 3， 2 27， 554号、 同第 3， 647, 291号、 同第 3 , 958, 993号、 同第 4， 4 19, 886号、 同第 3， 933， 500号、 特開昭 57-56 837号、 同 51— 13239号、 米国特許第 2， 072, 363号、 同第 2， 070， 266号、 RD40145の XIV項などに記載されているもの を挙げることができる。 また、 本発明で用いることができるカプラーの具体例は、 RD40145 の II項等に記載されている。 In the present invention, a DIR compound can be used. Specific examples of the DIR compound that can be used include, for example, D-1 to D-34 described in JP-A No. 4-114153, and the present invention preferably uses these compounds. . Specific examples of the DIR compound that can be used in the present invention include, in addition to the above, for example, US Pat. Nos. 4,234,678, 3,227,554, 3,647,291, and Nos. 3,958,993, 4,419,886, 3,933,500, JP-A-57-56837, 51-13239, U.S. Pat. No. 363, No. 2, 070, 266 and RD40145, section XIV can be mentioned. Specific examples of the coupler that can be used in the present invention are described in RD40145, section II and the like.
本発明で使用する添加剤は、 RD 40145の VIII項に記載されている分 散法などにより添加することができる。  The additives used in the present invention can be added by the dispersion method described in RD 40145, Section VIII.
本発明においては、 前述 RD 38957の XV項等に記載される公知の支 持体を使用することができる。  In the present invention, a known support described in RD 38957, section XV, and the like can be used.
本発明の撮影用ハロゲン化銀カラー写真感光材料には、 前述 RD 3895 7の XI項に記載されるフィルタ一層や中間層等の補助層を設けることがで きる。  The silver halide color photographic light-sensitive material for photography 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 38957, Section XI.
本発明の撮影用ハロゲン化銀カラー写真感光材料は、 前述 RD 38957 の XI項に記載の順層、 逆層、 ユニット構成等の様々な層構成を採ることが できる。  The silver halide color photographic light-sensitive material for photography of the present invention can have various layer constitutions such as a forward layer, a reverse layer, and a unit constitution described in Section XI of RD 38957.
本発明に係るハロゲン化銀乳剤は、 一般用、 プロフェッショナル用または 映画用の撮影用カラーネガフィルムに適用することができる。  The silver halide emulsion according to the present invention can be applied to color negative films for general, professional or cinematographic use.
本発明の撮影用ハロゲン化銀カラー写真感光材料は、 前記基準現像処理以 外でも現像処理することができる。 例えば、 T. H. ジエームズ著、 セオリ ィ ォプ ザ ホトグラフィック プロセス第 4版 （Th e Th e o r y o f Th e Ph o t o g r a p h i c P r o c e s s F o r t h E d i t i o n) 第 29 1頁一第 334頁及びジャーナル ォブ ザ ァメ リカン ケミカノレ ソサエティ （J o u r n a l o f t h e Am e r i c a n Ch em i c a l S o c i e t y) 第 73卷、 第 3, 100頁 (1951) に記載されている、 それ自体公知の現像剤を使用することがで き、また、前述の RD 38957の XVII〜XX項及び R D 40145の XXIII 項に記載された通常の方法によって、 現像処理することができる。 The silver halide color photographic light-sensitive material for photography of the present invention can be subjected to development processing other than the standard development processing. For example, see TH The James, Theory of the Photographic Process, 4th Edition, pp. 291-334, and the Journal of the American Chemistry Known developers described in the Society (Journalofthe American Chemical Society), vol. 73, p. 3, 100 (1951) can be used, and the aforementioned RD 38957 can be used. XVII to XX of RD 40145 and XXIII of RD 40145 The development can be performed by the usual method described in the section.
以下、 実施例を挙げて具体的に説明するが、 本発明はこれらに限定される ものではない。  Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
実施例 1  Example 1
〔試料 10 1の作製〕  [Preparation of Sample 101]
下引層を施した厚さ 1 20 mのトリァセチノレセルロースフィルム支持体 上に、 特開 2000— 8 9426公報の実施例 1に記載の試料 10 1におい て、 第 5層 （高感度赤感色性層） で用いた沃臭化銀乳剤 cに代えて下記乳剤 Aを、 第 9層 （高感度緑感色性層） で用いた沃臭化銀乳剤 Em— 1に代えて 下記乳剤 Bを、 第 1 2層 （高感度青感色性層） で用いた沃臭化銀乳剤 gに代 えて下記乳剤 Cを、 それぞれ用いた以外は同様にして、 試料 1 01を作製し た。  In the sample 101 described in Example 1 of JP-A-2000-89426, a fifth layer (highly sensitive red-sensitive layer) was placed on a 120-m-thick triacetylcellulose film support provided with an undercoat layer. The following emulsion A was used in place of the silver iodobromide emulsion c used in the color layer) and the following emulsion B was used in place of the silver iodobromide emulsion Em-1 used in the ninth layer (highly sensitive green color-sensitive layer). Sample 101 was prepared in the same manner except that the following emulsion C was used instead of the silver iodobromide emulsion g used in the first and second layers (highly sensitive blue-sensitive layer).
試料 10 1の作製に用いた各沃臭化銀乳剤の詳細を、 下表に示す。 乳剤 形状 円換算直径 転位線 粒径分布 沃化銀 ァス クト比 番号 ( β m; 変動係数 含有率  The details of each silver iodobromide emulsion used to prepare Sample 101 are shown in the table below. Emulsion shape Diameter in circles Dislocation lines Particle size distribution Silver iodide aspect ratio number (βm; Coefficient of variation Content
A 平板状 1. 4 26 % 6モル％ 8 . 0 A Plate form 1. 26% 6 mol% 8.0
B 平板状 1. 5 23 % 6モル％ 7 . 5B plate 1.53 23% 6mol% 7.5
C 平板状 1. 5 28 % 7モル％ 6 . 0 なお、 上記作製した試料 1 01の総塗布銀量は、 3. 2 7 g / m 2であつ た C tabular 1.5 28% 7 mol% 6.0 The total coated silver amount of the sample 1 01 prepared above may been filed with 3. 2 7 g / m 2
試料 10 1を、 J I S— K— 76 1 4 (1 98 1) に準じて露光し、 前記 基準現像処理を行った。 試料の透過 S t a t u sM濃度を測定し、 写真用 D -L o g E特性曲線を作成した。 Sample 10 1 was exposed according to JIS-K-76 14 (1 981). Reference development processing was performed. The transmission Status sM concentration of the sample was measured and a photographic D-LogE characteristic curve was created.
この特性曲線から得られた γ値および γ値バランスは、 赤光測光 γ値 = 0 . 6 5、 緑光測光 γ値 =0. 64、 青光測光 γ値 =0. 73、 赤光測光 y値 Z緑光測光 γ値 = 1. 0 2、 青光測光 γ値 Ζ緑光測光 y値 = 1. 14であつ た。  The γ value and γ value balance obtained from this characteristic curve are as follows: red light metering γ value = 0.65, green light metering γ value = 0.64, blue light metering γ value = 0.73, red light metering y value Z green light metering γ value = 1.02, blue light metering γ value Ζ green light metering y value = 1.14.
また、 赤感光性層、 緑感光性層の各高感度層、 中感度層、 低感度層の最大 濃度部の濃度割合を、 前述の方法で測定した結果を下表に示す。 最大濃度 （比率）  In addition, the following table shows the results of measuring the concentration ratio of the maximum density part of each of the high-sensitivity layer, the medium-sensitivity layer, and the low-sensitivity layer of the red-sensitive layer and the green-sensitive layer by the method described above. Maximum concentration (ratio)
低感度層  Low sensitivity layer
赤感光性層 8 25 5 7%  Red photosensitive layer 8 25 5 7%
緑感光性層 7 27 56 % 〔試料 102の作製〕  Green photosensitive layer 7 27 56% [Preparation of sample 102]
上記試料 1 0 1の作製において、 各感光性層の高感度層、 中感度層及ぴ低 感度層で用いた沃臭化銀乳剤の化学增感条件を、 下記の γ値及び γ値バラン スとなるように適宜調整して、 試料 102を作製した。  In the preparation of Sample 101 above, the chemical sensitivity conditions of the silver iodobromide emulsion used in the high-sensitivity layer, the medium-sensitivity layer, and the low-sensitivity layer of each photosensitive layer were determined by the following γ value and γ value balance. Sample 102 was produced by appropriately adjusting the values to be as follows.
試料 102の y値および γ値パランスは、 赤光測光 y値 =0. 5 8、 緑光 測光 γ値 =0. 60、 青光測光 γ値 =0. 6 3、 赤光測光 γ値/緑光測光 y 値 = 0. 9 7、 青光測光 γ値/緑光測光 γ値 = 1. 05であった。  The y value and γ value balance of sample 102 are as follows: red light metering y value = 0.58, green light metering γ value = 0.60, blue light metering γ value = 0.63, red light metering γ value / green light metering y value = 0.997, blue light metering γ value / green light metering γ value = 1.05.
また、 赤感光性層及び緑感光性層の最大濃度部の濃度割合は、 いずれも試 料 1 0 1と同じであった。 〔試料 1 0 3の作製〕 The concentration ratio of the maximum density part of the red photosensitive layer and the green photosensitive layer was the same as that of Sample 101. [Preparation of Sample 103]
上記試料 1 0 2の作製において、 第 5層、 第 9層、 第 1 2層で用いた沃臭 化銀乳剤 A、 B、 Cに代えて、 それぞれ下記沃臭化銀乳剤 D、 E、 Fを用い た以外は同様にして、 試料 1 0 3を作製した。 乳剤 形状 円換算直径 転位線 粒径分布 沃化銀 ァス ゥト比 番号 ( β m) 右 ίハκ、、 変動係数 含有率  In the preparation of Sample 102, the following silver iodobromide emulsions D, E, and F were used in place of the silver iodobromide emulsions A, B, and C used in the fifth, ninth, and second layers, respectively. Sample 103 was prepared in the same manner except that was used. Emulsion shape Circle-converted diameter Dislocation line grain size distribution Silver iodide paste ratio number (βm) Right ίC, Variation coefficient Content
D 平板状 1 . 4 .有 2 6 % 6モル0 /0 8 . 0D flat 1.4. Yes 2 6% 6 mole 0/0 8. 0
F 平板状 1 . 5 有 2 3 % 6モル％ 7 . 5 G 平板状 1 . 5 有 2 8 % 7モル0 /0 6 . 0 試料 1 0 3の作製においては、 γ値、 y値バランス及び各層の最大濃度部 の濃度割合は、 試料 1 0 2と同一になるように、 調製条件を適宜調整した。 〔試料 1 0 4の作製〕 F Flat 1.5% 23% 6mol% 7.5G Flat 1.5% 28% 7mol 0 / 06.0 In preparing sample 103, the γ value, y value balance and The preparation conditions were appropriately adjusted such that the concentration ratio of the maximum concentration part of each layer was the same as that of Sample 102. [Preparation of Sample 104]
上記試料 1 0 3の作製において、 各感光性層の高感度層、 中感度層及び低 感度層で用いた沃臭化銀乳剤の化学增感条件を、 下記の T値及び y値バラン スとなるように適宜調整して、 試料 1 0 4を作製した。  In the preparation of Sample 103 above, the chemical sensitivity conditions of the silver iodobromide emulsion used in the high-, middle-, and low-sensitivity layers of each photosensitive layer were adjusted to the following T value and y value balance. The sample was adjusted as needed to prepare Sample 104.
試料 1 0 4の γ値おょぴ γ値バランスは、 赤光測光 γ値 = 0 . 5 9、 緑光 測光 y値 = 0 . 5 9、 青光測光 γ値 == 0 . 6 6、 赤光測光 Ί値 緑光測光 Ί 値 = 1 . 0 2、 青光測光 値 緑光測光 γ値 = 1 . 1 4であった。 The γ value and γ value balance of sample 104 were as follows: red light metering γ value = 0.59, green light metering y value = 0.59, blue light metering γ value = 0.66, red light metering photometric Ί value green photometric Ί value = 1. 0 2, blue light photometric value green photometric γ value = 1. was 1 4.
また、 赤感光性層及び緑感光性層の最大濃度部の濃度割合は、 いずれも試 料 1 0 3と同じであった。  The concentration ratio of the maximum density part of the red photosensitive layer and the green photosensitive layer was the same as that of Sample 103.
〔試料 1 0 5の作製〕 上記試料 1 0 4の作製において、 第 5層、 第 9層、 第 1 2層で用いた沃臭 化銀乳剤 D、 E、 Fに代えて、 それぞれ下記沃臭化銀乳剤 G、 H、 Iを用い た以外は同様にして、 試料 1 0 5を作製した。 乳剤 形状 円換算直径 転位線 粒径分布 沃化銀 ァス ク卜 J 番号 ( μ mリ 有無 変動係数 含有率 [Preparation of Sample 105] In the preparation of Sample 104, the following silver iodobromide emulsions G, H, and I were used in place of the silver iodobromide emulsions D, E, and F used in the fifth, ninth, and second layers, respectively. Sample 105 was prepared in the same manner except that was used. Emulsion shape Diameter in circles Dislocation lines Particle size distribution Silver iodide J number (μm presence or absence Coefficient of variation Content
G 平板状 1 . 4 有 3 5 % 6モル0 /0 8 . 0G flat 1.4 Yes 3 5% 6 mole 0/0 8.0
H 平板状 1 . 5 有 3 1 % 6モル％ 7 . 5H Plate 1.5 1.5 Yes 3 1% 6mol% 7.5
I 平板状 1 . 5 有 3 9 % 7モル％ 6 . 0 試料 1 0 5の作製においては、 y値、 y値バランス及ぴ各層の最大濃度部 の濃度割合は、 試料 1 0 4と同一になるように、 調製条件を適宜調整した。 〔試料 1 0 6の作製〕 I Plate 1.5 Yes 39% 7mol% 6.0 In the preparation of Sample 105, the y-value, y-value balance and the concentration ratio of the maximum concentration part of each layer were the same as in Sample 104. Preparation conditions were adjusted appropriately so as to be as follows. [Preparation of Sample 106]
上記試料 1 0 5の作製において、 第 5層、 第 9層、 第 1 2層で用いた沃臭 化銀乳剤 G、 H、 Iに代えて、 それぞれ下記沃臭化銀乳剤】、 K、 Lを用い た以外は同様にして、 試料 1 0 6を作製した。 乳剤 形状 円換算直径 転位線 粒径分布 沃化銀 ァスぺクト比 番号 ( μ m) ハ、、 変動係数 含有率  In the preparation of Sample 105, silver iodobromide emulsions G, H, and I used in the fifth, ninth, and second layers were replaced with the following silver iodobromide emulsions], K, and L, respectively. Sample 106 was prepared in the same manner except that was used. Emulsion shape Diameter in circles Dislocation lines Particle size distribution Silver iodide aspect ratio number (μm) C, Coefficient of variation Content
J 平板状 1 . 4 有 3 5 % 3 . 5モノレ0 /0 8 . 0J tabular 1.4 Yes 3 5% 3.5 Monore 0/0 8.0
K 平板状 1 . 5 有 3 1 % 3 . 5モノレ0 /0 7 . 5K tabular 1.5 Yes 3 1% 3.5 Monore 0/0 7.5
L 平板状 1 . 5 有 3 9 % 4 . 0モル0 /0 6 . 0 試料 1 0 6の作製においては、 γ値、 γ値バランス及ぴ各層の最大濃度部 の濃度割合は、 試料 1 0 5と同一になるように、 調製条件を適宜調整した。 〔試料 1 0 7の作製〕 L tabular 1.5 Yes 3 9% 4.0 mol 0/0 6.0 In the preparation of Sample 106, the preparation conditions were appropriately adjusted so that the γ value, the γ value balance, and the concentration ratio of the maximum concentration portion of each layer were the same as those of Sample 105. [Preparation of Sample 107]
上記試料 1 0 6の作製において、 第 5層、 第 9層、 第 1 2層で用いた沃臭 化銀乳剤]"、 K、 Lに代えて、 それぞれ下記沃臭化銀乳剤 Μ、 Ν、 Οを用い た以外は同様にして、 試料 1 0 7を作製した。 乳剤 形状 円換算直径 転 nfe 粒径分布 沃化銀 ァス クト比 番号 A= ハ 変動係数 含有率  In the preparation of Sample 106 above, the following silver iodobromide emulsions Μ, Ν, and 銀, Ν, and 銀, 、, K, and 沃 were used in the fifth, ninth, and second layers, respectively. Sample 107 was prepared in the same manner except that Ο was used.Emulsion shape Circle-converted diameter conversion nfe grain size distribution Silver iodide aspect ratio number A = c Variation coefficient Content
Μ 平板状 1 . 4 有 1 2 % 6モル％ 8 . 0 平板 Flat plate 1.4 Yes 12% 6mol% 8.0
Ν 平板状 1 . 5 有 1 0 % 6モル％ 7 . 5Ν Flat 1.5 Yes 10% 6mol% 7.5
Ο 平板状 1 . 5 有 1 4 % 7モル％ 6 . 0 試料 1 0 7の作製においては、 γ値、 γ値バランス及ぴ各層の最大濃度部 の濃度割合は、 試料 1 0 6と同一になるように、 調製条件を適宜調整した。 〔試料 1 0 8の作製〕 平板 Plate 1.5 1.5% 14% 7mol% 6.0 In the preparation of sample 107, the γ value, γ value balance and the concentration ratio of the maximum density part of each layer were the same as in sample 106. Preparation conditions were adjusted appropriately so as to be as follows. [Preparation of Sample 108]
上記試料 1 0 7の作製において、 第 5層、 第 9層、 第 1 2層で用いた沃臭 化銀乳剤 Μ、 Ν、 Οに代えて、 それぞれ下記沃臭化銀乳剤 P、 Q、 Rを用い た以外は同様にして、 試料 1 0 8を作製した。 乳剤 形状 円換算直径 転位線 粒径分布 沃化銀 ァスぺク ト比 番号 ( β m ) ハ、、 変動係数 含有率 In the preparation of Sample 107, the following silver iodobromide emulsions P, Q, and R were used in place of the silver iodobromide emulsions Μ, Ν, and 用 い used in the fifth, ninth, and second layers, respectively. A sample 108 was prepared in the same manner except for using. Emulsion shape Circle-converted diameter Dislocation line grain size distribution Silver iodide aspect ratio number (βm) C, Coefficient of variation Content
P 平板状 1 . 4 有 1 2 % 3 . 5モル0 /0 8 . 0P tabular 1.4 Yes 1 2% 3. 5 mole 0/0 8.0
Q 平板状 1 . 5 有 1 0 % 3 . 5モル0 /0 7 . 5Q tabular 1.5 Yes 1 0% 3. 5 mole 0/0 7.5
R 平板状 1 . 5 有 1 4 % 4 . 0モル0 /0 6 . 0 試料 1 0 8の作製においては、 γ値、 y値バランス及び各層の最大濃度部 の濃度割合は、 試料 1 0 7と同一になるように、 調製条件を適宜調整した。 〔試料 1 0 9の作製〕 R Plate 1.5 1.5% 4.0 mol 0 / 06.0 In preparing sample 108, the γ value, y value balance, and the concentration ratio of the maximum concentration portion of each layer were as follows. The preparation conditions were adjusted as appropriate so as to be the same. [Preparation of Sample 109]
上記試料 1 0 8の作製において、 第 5層、 第 9層、 第 1 2層で用いた沃臭 化銀乳剤 P 、 Q、 Rに代えて、 それぞれ下記沃臭化銀乳剤 S 、 T、 Uを用い た以外は同様にして、 試料 1 0 9を作製した。 乳剤 形状 円換算直径 車位線 粒径分布 沃化銀 ァスぺクト比 番号 ( β m. ) ハ、、 変動係数 含有率  In the preparation of Sample 108, the following silver iodobromide emulsions S, T, and U were used in place of the silver iodobromide emulsions P, Q, and R used in the fifth, ninth, and second layers, respectively. A sample 109 was prepared in the same manner except for using. Emulsion shape Circle-converted diameter Diameter curve Grain size distribution Silver iodide aspect ratio number (βm.) C, Coefficient of variation Content
S 平板状 1 . 4 有 2 6 % 3 . 5モノレ( % 8 . 0 S Flat 1.4 Yes 26% 3.5 Monole (% 8.0
T 平板状 1 . 5 有 2 3 % 3 . 5モノレ ( % 7 . 5T Flat 1.5 Yes 23% 3.5 Monole ( % 7.5
U 平板状 1 . 5 有 2 8 % 4 . 0モノレ ( % 6 . 0 試料 1 0 9の作製においては、 γ値、 V値バランス及び各層の最大濃度部 の濃度割合は、 試料 1 0 8と同一になるように、 調製条件を適宜調整した。 〔試料 1 1 0 、 1 1 1の作製〕 U Flat 1.5% 28% 4.0 monolith ( % 6.0 In preparing sample 109, the γ value, V value balance, and the concentration ratio of the maximum density part of each layer were the same as that of sample 108. The preparation conditions were adjusted as appropriate so that they were identical [Preparation of Samples 110 and 111]
試料 1 0 9の作製において、 下表の様に各感光性層のハロゲン化銀乳剤の 塗布銀量 （g/m2) を変更した以外は同様にして、 試料 0 を 作製した。 各層の塗布銀量 （gZm2) In the preparation of Sample 109, the silver halide emulsion of each photosensitive layer was Sample 0 was prepared in the same manner except that the amount of applied silver (g / m 2 ) was changed. Silver coating amount of each layer (gZm 2 )
試料 10 9 試料 1 1 0 試料 1 1 1 第 3層 0. 2 9 0. 24 0. 3 8 第 4層 0. 2 8 0. 23 0. 3 7  Specimen 10 9 Specimen 1 1 0 Specimen 1 1 1 3rd layer 0.29 0.24 0.33 4th layer 0.28 0.23 0.23 7
0. 5 5 0. 47 0. 6 7 0.5 0.5 0 0.47 0.6 0.7
0. 2 4 0. 20 0. 3 3 第 8層 0. 3 5 0. 30 0. 4 5 第 9層 0. 3 8 0. 3 2 0. 4 8 第 1 1層 0. 3 1 0. 25 0. 4 0 第 1 2層 0. 4 6 0. 38 0. 5 7 総塗布銀量 3. 2 7 2. 80 4. 0 6 試料 1 1 0 1 1 1の作製においては、 γ値、 γ値バランス及び各層の最 大濃度部の濃度割合は、 試料 109と同一になるように、 調製条件を適宜調 整した。 0.24 0.20 0.3 3 8th layer 0.35 0.30 0.45 5th layer 0.38 0.3 2 0.4 8 1st layer 0.3 1 0. 25 0.40 First layer 2 0.4 6 0.38 0.57 Total silver coating 3.2 7 2.80 4.06 In the preparation of sample 1 1 0 1 1 1 The preparation conditions were appropriately adjusted so that the γ value balance and the concentration ratio of the maximum concentration part of each layer were the same as those of Sample 109.
〔試料 1 1 2 1 1 3の作製〕  [Preparation of sample 1 1 2 1 1 3]
試料 109の作製において、 第 3 5層、 第 7 9層の各層ハロゲン化銀 乳剤の塗布銀量を適宜調整して、 最大濃度部の濃度割合が下表になるように 変更した以外は同様にして、 試料 1 1 2 1 1 3を作製した。 〈試料 1 1 2〉 In the preparation of Sample 109, the procedure was the same except that the silver coating amount of the silver halide emulsions of the 35th and 79th layers was adjusted appropriately and the concentration ratio of the maximum density part was changed as shown in the table below. As a result, a sample 1 1 2 1 1 3 was prepared. <Sample 1 1 2>
最大濃度 （比率）  Maximum concentration (ratio)
中感度層  Medium sensitivity layer
赤感光性層 25 % 3 5 % 40 %  Red photosensitive layer 25% 35% 40%
緑感光性層 25 % 3 5 % 40%  Green photosensitive layer 25% 35% 40%
〈試料 1 1 3〉 <Sample 1 1 3>
最大濃度 （比率）  Maximum concentration (ratio)
中感度層  Medium sensitivity layer
赤感光性層 8 % 3 2 60  Red photosensitive layer 8% 3 2 60
緑感光性層 8 % 3 2 60 試料 1 1 2、 1 1 3の作製においては、 γ値及び y値バランスは、 試料 1 09と同一になるように、 調製条件を適宜調整した。  Green photosensitive layer 8% In preparation of 3260 samples 112 and 113, the preparation conditions were appropriately adjusted so that the γ value and the y value balance were the same as in sample 109.
〔各試料の特性評価〕  [Evaluation of characteristics of each sample]
以上のようにして作製した試料 10 1 ~ 1 1 3について、 下記の方法に従 つて、 現像処理安定性の評価 （a)、 （b)、 (c) を行なった。 , 〈評価一 a〉 ' 各試料にステップゥエッジ露光を施した後、 前述の基準現像処理における 発色現像工程の処理時間として、 基準現像時間と、 基準現像時間に対し ± 1 5秒変化させた各現像処理を行い、 基準現像時間での緑光測光濃度 1. 0の 濃度点対応する露光点で、 現像時間が + 1 5秒処理試料の同濃度 De (+ 1 5 S) と、 現像時間が一 15秒処理試料の同濃度 De (- 1 5 S) とを測定 し、 その濃度差 （ADG) を求めた。 ADGが小さいほど優れていることを表 す。 The samples 101 to 113 prepared as described above were evaluated for development processing stability (a), (b), and (c) according to the following method. , <Evaluation 1a>'After subjecting each sample to step ゥ edge exposure, the processing time of the color development step in the above-mentioned standard development process was changed by the standard development time and ± 15 seconds from the standard development time. Perform each development process, and at the exposure point corresponding to the density point of green light photometric density of 1.0 at the standard development time, the development time is +15 seconds, and the same density D e (+15 S) of the processed sample and the development time Measured the same concentration D e ( -15 S) of the treated sample for 15 seconds. Then, the concentration difference (AD G ) was obtained. To the table that the AD G is better smaller.
〈評価 _b〉  <Evaluation _b>
各試料にステップゥエッジ露光を施した後、 自動現像処理機を用いて、 処 理面積に従って補充液を規定量補充しながら連続処理 （ランニング処理） を 行い、 処理安定性の評価を行った。 前述の基準現像処理において、 処理開始 時の現像液での緑光測光感度 SG。と、 1/2ラウンドのランニング処理を行 つた後の緑光測光感度 Sei/2を測定し、 下式に従って感度変動率 Scを求め た。 Scは、 値が 1. 0に近いほど優れていることを表す。After subjecting each sample to step-to-edge exposure, continuous processing (running processing) was performed using an automatic processor while replenishing a specified amount of replenisher according to the processing area, and processing stability was evaluated. In the reference development process described above, the green light photometric sensitivity S G in the developer at the start of the process. Then, the green light photometric sensitivity S ei / 2 after performing the 1/2 round running process was measured, and the sensitivity variation rate Sc was obtained according to the following equation. S c indicates that the closer the value is to 1.0, the better.
Figure imgf000020_0001
Figure imgf000020_0001
なお、 本発明でいう 1 / 2ラウンドとは、 発色現像液補充量の積算量が、 該発色現像液の処理槽容積の 1Z2に達した時点を意味する。 また、 緑光測 光感度は、 最小濃度 +0. 3の濃度を得るに要する露光量の逆数として表示 した。  In the present invention, “ラ ウ ン ド round” means a point in time when the integrated amount of the replenishment amount of the color developing solution reaches 1Z2 of the processing tank volume of the color developing solution. The green photometric sensitivity was expressed as the reciprocal of the exposure required to obtain a density of minimum density +0.3.
〈評価一 c〉  <Evaluation one c>
各試料にステップゥエッジ露光を施した後、 発色現像液組成中の発色現像 主薬である 4ーァミノ _ 3—メチルー N— ( ーヒ ドロキシェチル） ァニリ ン硫酸塩の添加量を、 基準処理量に対して ± 20%変化させた発色現像液を 調製し、 現像処理を行った。 基準現像処理での赤光測光濃度 1. 0の濃度に 対応する露光量点で、 発色現像主薬 + 20 %の発色現像液での赤光測光濃度 DR + 2。と、 発色現像主薬一 20%の発色現像液での赤光測光濃度 DR—2。と の濃度差 （ADR) を求めた。 ADRは、 値が小さいほど優れていることを表 す。 以上の様にして測定した各評価結果を、 下表に示す c 現像処理安定性の評価 After subjecting each sample to step ゥ edge exposure, add the amount of 4-amino-3-methyl-N-(-hydroxyxethyl) aniline sulfate, which is the color developing agent in the color developing solution composition, to the standard processing amount. A color developing solution was prepared with a change of ± 20% and developed. In exposure point corresponding to the concentration of the red light photometric density 1.0 at the reference development, red light metering concentration with a color developer + 20% of the color developing solution D R + 2. When the red light photometric density D R of the color developing agent one 20% of the color developing solution - 2. The concentration difference (AD R ) between and was determined. AD R is to table the superiority Smaller values. Each evaluation results, the evaluation of c developing stability shown in the following table were measured in the manner described above
口 ィ-^ Λ D Q ( \ Mouth- ^ Λ D Q (\
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ダ J 丄 U Z υ . υ y U . y D 1 o レ ifef : τηί  Y U. Y D 1 o レ ifef: τηί
J¾率 5?1タ y 丄 U o π U · υ ο -Jr- ¾ HR  J¾ rate 5 to 1 tab y 丄 U o π U · υ ο -Jr- ¾ HR
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Figure imgf000021_0001
ZU
106 0. 03 1. 01 0. 07 本発明106 0.03 1.01 0.07 The present invention
107 0. 04 1. 02 0 · 06 本発明107 0.04 1.02 006
108 0. 03 1. 00 0. 04 本発明108 0.03 1.00 0.04 The present invention
109 0， 02 1， 00 0. 03 本発明109 0, 02 1, 00 0. 03 The present invention
110 0. 03 0. 99 0. 04 本発明110 0.03 0.99 0.04 The present invention
111 0. 04 0. 99 0. 05 本発明111 0.04 0.99 0.05 The present invention
112 0. 03 1. 00 0. 06 本発明112 0.03 1.00 0.06 The present invention
113 0. 03 1， 01 0. 06 本発明 産業上の利用の可能性 113 0. 03 1, 01 0. 06 INDUSTRIAL APPLICABILITY
以上のように、 本発明の構成により、 好ましい軟調な階調を有すると共に 、 現像処理液の活性度 （現像時間、 連続処理及び現像主薬濃度等の変動） に 対する現像処理安定性に優れている撮影用ハ口ゲン化銀力ラ 写真感光材料 を提供することができる。  As described above, the configuration of the present invention has a preferable soft gradation and excellent development processing stability with respect to the activity of the developing solution (development time, continuous processing, and fluctuations in the concentration of the developing agent). A photographic light-sensitive material can be provided.

Claims

請求の範囲 The scope of the claims
1. 支持体上にそれぞれ同一感色性で感度の異なる少なくとも 2層からな る赤感光性層、 緑感光性層、 青感光性層と非感光性層とを有する撮影用ハロ ゲン化銀カラー写真感光材料において、 基準現像処理での y値が下記のいず れの条件も満たし、かつ各感光性層の少なくとも 1層が、全投影面積の 50% 以上のハロゲン化銀粒子が転位線を有する平板状ハロゲン化銀乳剤を含有す ることを特徴とする撮影用ハ口ゲン化銀力ラー写真感光材料。 1. A silver halide color for photography having at least two red, green, and blue light-sensitive layers and a non-light-sensitive layer each having at least two layers having the same color sensitivity and different sensitivities on a support. In a photographic light-sensitive material, the y value in the standard development process satisfies any of the following conditions, and at least one of the photosensitive layers has silver halide grains having a dislocation line of 50% or more of the total projected area. A silver halide photographic light-sensitive material for photographing, comprising a tabular silver halide emulsion having a silver halide emulsion.
赤光測光 γ値 = 0. 5 5〜 0. 6 3  Red light metering γ value = 0.5 5 to 0.6 3
緑光測光 γ値 =0. 54〜0. 6 2  Green light metering γ value = 0.54 to 0.62
青光測光 γ値 =0. 6 2〜0. 70  Blue light metering γ value = 0.6 2 to 0.70
ただし γ値とは、 写真用 D (濃度） 一 L o g E (露光量） からなる特性曲 線上において、 最小濃度値 +0. 3の点と、 該点に対応する露光量の 1 0倍 量に対応する露光量点における濃度点とを結ぶ直線の傾き （t a n 0) と定 義する。  Here, the γ value is defined as the point of minimum density value +0.3 on the characteristic curve consisting of D (density) for photo and Log E (exposure amount), and 10 times the exposure amount corresponding to the point. Is defined as the slope (tan 0) of the straight line connecting the density point at the exposure point corresponding to.
2. 前記各 γ値が、 下記のいずれの条件も満たすことを特徴とする請求の 範囲第 1項に記載の撮影用ハ口ゲン化銀力ラ一写真感光材料。  2. The photographic material according to claim 1, wherein each of the γ values satisfies any of the following conditions:
赤光測光 γ値ノ緑光測光 y値 = 1. 00〜1. 04  Red light metering γ value Green light metering y value = 1.00 to 1.04
青光測光 γ値 Z緑光測光 Y値 = 1. 1 2〜1. 1 6  Blue light metering γ value Z Green light metering Y value = 1.12 to 1.16
3. 前記平板状ハロゲン化銀乳剤が、 円換算直径の粒径分布の変動係数 が 1 5〜 30 %であることを特徴とする請求の範囲第 1項又は第 2項に記載 の撮影用ハ口ゲン化銀力ラ一写真感光材料。 3. The photographing device according to claim 1, wherein the tabular silver halide emulsion has a variation coefficient of a particle size distribution of a circle-equivalent diameter of 15 to 30%. Silver sensitized silver photographic material.
4. 前記平板状ハロゲン化銀乳剤が、 平均沃化銀含有率が 5. 0モル％以 下であることを特徴とする請求の範囲第 1項から第 3項のいずれか 1項に記 載の撮影用ハロゲン化銀カラー写真感光材料。 4. The tabular silver halide emulsion has an average silver iodide content of 5.0 mol% or less. The silver halide color photographic light-sensitive material for photography according to any one of claims 1 to 3, wherein the material is:
5. 総塗布銀量が、 3. O g/m2以上、 4. 0 gZm2以下であることを 特徴とする請求の範囲第 1項から第 4項のいずれか 1項に記載の撮影用ハ口 ゲン化銀カラー写真感光材料。 5. The photographing method according to any one of claims 1 to 4, wherein the total applied silver amount is 3.O g / m 2 or more and 4.0 gZm 2 or less. Haguchi Silver halide color photographic light-sensitive material.
6. 前記赤感光性層と緑感光性層とが、 それぞれ高感度層、 中感度層、 及 び低感度層の 3層からなり、かつ基準現像処理での最大濃度部の濃度割合が、 該高感度層が 1 0〜 20 %、 該中感度層が 10〜 30 %、 該低感度層が 50 〜 80 %の範囲内にあることを特徴とする請求の範囲第 1項から第 5項のい ずれか 1項に記載の撮影用ハロゲン化銀カラー写真感光材料。  6. The red-sensitive layer and the green-sensitive layer are each composed of three layers of a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer, and the density ratio of the maximum density part in the reference development processing is as follows. The high-sensitivity layer is in the range of 10 to 20%, the medium-sensitivity layer is in the range of 10 to 30%, and the low-sensitivity layer is in the range of 50 to 80%. Any of the silver halide color photographic light-sensitive materials for photography according to item 1.
PCT/JP2002/007524 2002-07-25 2002-07-25 Silver halide color-photographic sensitive material for photography WO2004012011A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843369A (en) * 1969-04-17 1974-10-22 Fuji Photo Film Co Ltd Multi-layer color photographic light-sensitive materials
JPH09179255A (en) * 1995-12-26 1997-07-11 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JP2000089426A (en) * 1998-09-16 2000-03-31 Konica Corp Image forming method of silver halide color photographic sensitive material
JP2001092088A (en) * 1999-09-22 2001-04-06 Konica Corp Silver halide color photographic sensitive material and image forming method for same
JP2001133922A (en) * 1999-11-04 2001-05-18 Konica Corp Silver halide color photographic sensitive material and image forming method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843369A (en) * 1969-04-17 1974-10-22 Fuji Photo Film Co Ltd Multi-layer color photographic light-sensitive materials
JPH09179255A (en) * 1995-12-26 1997-07-11 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JP2000089426A (en) * 1998-09-16 2000-03-31 Konica Corp Image forming method of silver halide color photographic sensitive material
JP2001092088A (en) * 1999-09-22 2001-04-06 Konica Corp Silver halide color photographic sensitive material and image forming method for same
JP2001133922A (en) * 1999-11-04 2001-05-18 Konica Corp Silver halide color photographic sensitive material and image forming method

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