JP2618706B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic material (hereinafter abbreviated as a color photographic material), and particularly to a high-sensitivity color photographic material. The present invention also relates to a technique for improving performance deterioration such as increase in fog and deterioration in graininess when a photosensitive material is aged for a long time after production.

(Prior Art) In the field of silver halide color photographic light-sensitive materials, color photographic materials having an ISO display sensitivity exceeding 400 or 1000 have recently been put on the market due to advances in various technologies. Photographs with even higher sensitivity are required for shooting without a strobe in a dark room, shooting with a high-speed shutter using a telephoto lens for sports photography, and photography requiring long exposure such as astrophotography. ing. Increasing the photographic area by increasing the sensitivity of photosensitive materials is a theme imposed on the industry.

Many efforts have been made to increase the sensitivity of photosensitive materials. Numerous studies have been made on grain formation methods such as the shape, structure and composition of silver halide grains, chemical sensitization, spectral sensitization, additives, coupler structures and the like, and useful inventions have been made. However, the demand for high-sensitivity light-sensitive materials is greater than the advance of technology, and these methods alone have not been sufficient. Therefore, in order to achieve the object of increasing the sensitivity, it is a common practice in the art to produce a high-sensitivity photosensitive material by using a method of increasing the size of silver halide emulsion grains in combination with other techniques. However, increasing the size of silver halide emulsion grains increases sensitivity to some extent, but inevitably reduces the number of silver halide emulsion grains as long as the silver halide content is kept constant.
Therefore, there is a major drawback that the number of development start points is reduced and graininess is deteriorated. In order to compensate for this disadvantage, two silver halide emulsions having the same color sensitivity and sensitivity, that is, different silver halide emulsion grain sizes, as described in British Patent No. 923,045 and JP-B-49-15495, are used. A light-sensitive material having the above emulsion layer, a method using a high-speed reactive coupler as described in JP-A-55-62454, etc., U.S. Pat.
So-called DIR couplers described in 632,435 and the like, methods using DIR compounds, methods using couplers that produce mobile dyes described in British Patent No. 2,083,640, and JP-A-60-128443. A method using the described silver halide having a high average silver iodide content is known.
Each of these methods is an excellent invention having a great effect, but it is insufficient for the strict demand for a photosensitive material having high sensitivity and high image quality. Therefore, in order to increase the size of silver halide emulsion grains and at the same time increase the number of development starting points even slightly, high-sensitivity color light-sensitive materials are within the allowable range of desilvering properties during bleach-fix processing. The design has been made by increasing the content of silver halide emulsion grains.

However, it has been found that the high-sensitivity and high-quality photosensitive materials thus produced have the following undesirable disadvantages. This is a problem with storage stability over time that photographic performance deteriorates such as an increase in fog and deterioration of graininess between the production and use of the photosensitive material. That is, a photosensitive material having high sensitivity and high image quality immediately after production, fog increase, grain deterioration, and further decrease in sensitivity due to aging over half a year and one year,
This is a serious problem in practical use.

The fog increase due to the aging of the photosensitive material for a long time is usually caused by heat and humidity, but in the case of high-sensitivity photosensitive materials, fog increase due to γ-rays and cosmic rays called environmental radiation is another problem. It has been reported that Since the deterioration of the image quality due to the environmental radiation becomes more remarkable as the sensitivity of the photosensitive material becomes higher, it is necessary to take some measures for designing the photosensitive material having high sensitivity. However, according to our recent research,
It has been found that factors other than heat, humidity, environmental radiation, etc., increase the fog of the photosensitive material.
As a result of intensive studies, we have found that potassium ions contained in the photosensitive material are the cause. It is quite surprising that potassium ions are usually contained in a considerable amount in a light-sensitive material, and that the potassium ions cause deterioration of performance over time of the light-sensitive material.

Potassium ions contained in the light-sensitive material are used as Kcl, KBr, KI used when forming silver halide grains, adjusting pAg, etc., or when contained in gelatin, dyes, various additive chemicals, etc. Introduced into the material. Therefore, unless measures are taken to reduce potassium ions intentionally, the photosensitive material will contain a considerable amount of potassium ions. This is because the light-sensitive material itself has a factor that deteriorates the storage stability of the light-sensitive material over time, which is not preferable. However, until now, it has been unexpected that such an action as potassium ion is not performed. Therefore, no particular measure has been taken for the amount of potassium ion in the photosensitive material, which is a serious problem. is there.

(Problems to be Solved by the Invention) An object of the present invention is to firstly provide a silver halide color photographic light-sensitive material having high image quality, and secondly, increase the fog and the granularity when the light-sensitive material is aged. An object of the present invention is to provide a silver halide color photographic light-sensitive material in which deterioration of photographic performance such as deterioration is minimized.

(Means for Solving the Problems) The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, and the total amount of potassium ions contained in the light-sensitive material. the reaction but is at 20 mg / m ² or less, and a total amount 3.0~9.0g / m ² of all silver contained in the photosensitive material, an oxidation product of at least one layer a color developing agent in the silver halide emulsion layer The compound that releases the development inhibitor or its precursor and / or the compound that has been cleaved after reacting with the oxidized form of the color developing agent further reacts with the oxidized form of the color developing agent to cleave the development inhibitor or its precursor. Silver halide color photographic material characterized by having a specific photographic sensitivity of 320 or more containing a compound (hereinafter referred to as a "development inhibitor releasing compound"). It was made.

 Hereinafter, a specific configuration of the present invention will be described in detail.

In the present invention, when the amount of potassium ion per unit area of the photosensitive material exceeds 20 mg / m ² , fog increase and deterioration of granularity over time become remarkable, and the object of the present invention cannot be achieved. In the present invention, the amount of potassium ions contained per unit area of the light-sensitive material must be 20 mg / m ² or less.

Several methods are known for analyzing the amount of potassium ions contained in the light-sensitive material, for example, an analysis by an atomic absorption method. The analysis by the atomic absorption method is a simple method since the film may be cut out and wet-ashed with a mixed acid of sulfuric acid and nitric acid and then diluted with water for measurement. In order to analyze the amount of silver contained in the light-sensitive material, a method using fluorescent X-rays which can be cut out of a film and subjected to direct measurement is simple, but it can be analyzed by an atomic absorption method or the like. Good.

Photosensitive materials are very complex systems and contain many compounds. For example, to prepare one emulsion, silver nitrate, alkali halide, gelatin, silver halide solvent,
Dozens of compounds such as acids, alkalis, precipitants, chemical sensitizers, spectral sensitizers, antifoggants, stabilizers, thickeners, and preservatives are usually used. A color coupler, which is essential as a dye-forming substance, is added to a color photographic light-sensitive material. These are generally prepared and added as an emulsion using gelatin, an oil organic solvent, or the like, and usually 10 or more compounds are used to form one emulsion.

Color photography materials consist of about 15 hydrophilic colloid layers, each of which contains one or several emulsions, emulsions and various additives, hardeners, coating aids, etc. Have been. Therefore, a large number of compounds are used to produce one photosensitive material, and among these compounds, a large number of compounds containing potassium ions are included. Therefore, in order to reduce the amount of potassium ions in the photosensitive material, it is necessary to review these compounds and replace them with compounds containing no potassium ions.

Examples of the compound containing a potassium ion include the following. Kcl, KBr, and KI are the most commonly used compounds as alkali halides used in forming silver halide emulsion grains, because they are inexpensive and easily available in high purity. The pAg and pH of the emulsion,
Alternatively, it is very common to use KBr, KNO ₃ and KOH for adjusting the salt concentration. Gelatin also contains potassium ions, although the content varies depending on the type of gelatin.
In addition to these, many compounds containing a potassium ion as a counter ion such as a thickener, a spectral sensitizer, a stabilizer, an antifoggant, and a color coupler are used. In order to achieve the object of the present invention, it is necessary to replace these compounds with compounds which are inexpensive, have high purity and do not contain potassium ions, and further adjust the change in photographic performance caused by the replacement.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

Further, silver halide grains having a crystal plane defined by Miller index (nn1) (n ≧ 2, n is a natural number) on the outer surface as described in JP-A-86-9598 are also preferably used.

The grain size of the silver halide may be fine grains of about 0.1 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is described, for example, in Research Disclosure (RD), No. 17643 (1978).
December, p. 22-23, "I, Emulsion Production (Emulsion prepa
ration and types) ”and No. 18716 (November 1979
Mon), p.648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique P
hotographique Paul Montel, 1967), Photographic Emulsion Chemistry by Daffin, published by Focal Press (GFDuffin, Photo)
graphic Emulsion Chemistry (Focal Press, 1966)),
"Manufacture and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VLZelikman et al. Making and Coating).
Photographic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gatoff, Gutoff, Photographic Science and Engineerin.
g), 14, 248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The silver halide grains may be obtained by any of an acidic method, a neutral method, and an ammonia method, and a method of reacting a soluble silver salt with a soluble halide salt includes a one-side mixing method, a simultaneous mixing method, and a combination thereof. Any of these may be used. Further, a method of forming silver halide grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide grains are formed (a so-called controlled double jet method) can also be used.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide, such as, for example, rhodan silver or lead oxide.

Further, a mixture of grains having various crystal forms may be used, or two or more kinds of silver halide emulsions formed separately may be used as a mixture.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, and the like may be used in the course of silver halide grain formation or physical ripening.

Reduction sensitization nuclei may be formed on silver halide grains by a low pAg atmosphere, a high pH atmosphere, a method using an appropriate reducing agent, or a combination thereof. The reduction sensitization nucleus may be formed inside the grain, on the grain surface, or both.

Further, silver halide emulsions grown in the presence of tetrazaindene as described in JP-A-61-14630 and JP-A-60-122935 have high silver iodide content and excellent monodispersibility. Therefore, it is preferably used as a silver halide emulsion used in the present invention because it exhibits high sensitivity and excellent graininess.

Further, as shown in JP-A-58-126526, a silver halide emulsion which has been subjected to gold sulfur sensitization or gold selenium sensitization in the presence of a nitrogen-containing heterocyclic compound exhibits high fog and high sensitivity. Therefore, it is preferably used as a silver halide emulsion used in the present invention.

The emulsion is usually subjected to removal of soluble salts after precipitation or physical ripening, and as a means for this purpose, a known method of gelling gelatin, such as the Nudel washing method, may be used. Utilizing inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (eg, polystyrene sulfonic acid), or gelatin derivatives (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flourescence) may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives which can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

A color photographing material is usually composed of about 15 hydrophilic colloid layers, and the coating amount of the emulsion and the emulsion per unit area of the photosensitive material is relatively large. Since potassium ions are contained in an emulsion or an emulsion and introduced into the light-sensitive material, the amount of potassium ions in the light-sensitive material increases in correlation with the amounts of the emulsion and the emulsion. Therefore, it is very preferable to apply the present invention to color photographic materials.

As described above, high-sensitivity color light-sensitive materials have been designed to increase the content of silver halide grains due to the large size of silver halide grains. This leads to an increase in the amount of ions. In addition, the deterioration of performance of the color light-sensitive material over time becomes more remarkable as the sensitivity becomes higher. Therefore, the higher the sensitivity of the photosensitive material to which the effect of the present invention is also applied, the more remarkable,
The color photographic material to which the present invention is applied has a specific photographic sensitivity of 320.
It is necessary to be at least, but it is preferable to be at least 800.

The specific photographic sensitivity is determined as follows. The photosensitive material is exposed to a wedge according to a conventional method for measuring sensitometric performance, and then processed by the processing method described in Example 1. The processed sample was measured by sensitometry with blue, green and red light, and the exposure corresponding to the density 0.15 higher than the minimum density was expressed in lux seconds.
H _B, and H _G, H _R, further the larger value among H _B and H _R (the lower sensitivity) and H _S. At this time, specific photo sensitivity S
Is defined by the following equation.

Therefore, the higher the value of the specific photographic sensitivity S, the higher the sensitivity of the sample.

By the way, in high-sensitivity color light-sensitive materials, as described above, and as described in, for example, Japanese Patent Application Laid-Open No. 58-147,744, the content of silver halide emulsion grains is improved in order to improve the granularity even a little. Designing as much as possible has been the traditional practice in the industry. However it reviews the common sense in terms of performance degradation over time, severe performance degradation over time when the silver content exceeds 9.0 g / m ^2, a significant difference as compared with immediately after manufacture when it is actually used I found out. Surprisingly, when the silver content exceeds a certain level or more, the effect of improving the graininess originally intended is small.For example, in the performance after one year of aging, the one with a smaller silver content deteriorates with time. The reversal phenomenon was found that the graininess was much better due to the small amount of.

The amount of silver contained in the color light-sensitive material of the present invention is 3.0 g / m ²
It is necessary to be not less than 9.0 g / m ² . The preferred range of silver content the layer structure of the photosensitive material, vary somewhat due coupler species used, about half a year when the silver content in a specific photographic sensitivity 320 or more light-sensitive material exceeds 9.0 g / m ² to 2
The performance deteriorates to a degree that causes a problem in practical use over time of the year. Further, when the silver content is less than 3.0 g / m ² , the maximum density required for the color photographic material cannot be secured. Therefore, the silver content in the photosensitive material of the present invention is
It is necessary to be 3.0 g / m ² or more and 9.0 g / m ² or less, and 3.0 g / m ²
Is preferably at least 8.5 g / m ² or less, 3.0 g / m ² or more and 8.
More preferably, it is 0 g / m ² or less.

Thus, by reducing the amount of potassium ions and limiting the amount of silver, the performance deterioration of the high-sensitivity color light-sensitive material over time is improved. However, as described above, when the amount of silver is reduced, the deterioration with the lapse of time is improved. However, immediately after the production, the image quality is naturally deteriorated due to the deterioration of the graininess. This is insufficient for the purpose of providing a high-quality silver halide color light-sensitive material, and is inconvenient.
Therefore, in order to provide a silver halide color photographic material having high image quality and little deterioration in performance over time, in addition to the above-mentioned means for improving deterioration over time, it is necessary to improve the image quality immediately after production as much as possible. It is necessary to take the following measures.

As a method for improving the graininess, it is very common to use a development inhibitor releasing compound. The development inhibitor-releasing compound can be broadly classified according to the diffusivity of the released development inhibitor. Those compounds having diffusivity are referred to as diffusible development inhibitor-releasing compounds, and those having no diffusivity are referred to as non-diffusible development inhibitors. It can be a release compound. The diffusible development inhibitor-releasing compound is very useful from the viewpoint of color reproduction because a large layering effect can be obtained due to the diffusivity of the development inhibitor. By using these development inhibitor-releasing compounds in combination with the reduction of the amount of potassium ion and the amount of silver, it was possible to obtain a photosensitive material in which the granularity immediately after production was improved and the performance deterioration with time was suppressed to a small extent. But there was an unexpected effect here. That is, the diffusible development inhibitor-releasing compound was more effective than the non-diffusible development inhibitor-releasing compound in suppressing the deterioration of image quality over time. This mechanism has not been elucidated yet, and further research is needed.

Therefore, in order to obtain a silver halide color photographic light-sensitive material having high image quality and small performance deterioration with the lapse of time, which is the object of the present invention, it is necessary to carry out development together with means for reducing the amount of potassium ions and silver in the photographic material. Although it is necessary to use an inhibitor releasing compound, it is more preferable to use a diffusible development inhibitor releasing compound. Further, a diffusible development inhibitor releasing compound and a non-diffusible development inhibitor releasing compound may be used in combination.

"Development inhibitor releasing compound" used in the present invention
Is preferably represented by the following general formula (I).

Formula (I) A- (L ₁ ) _l- (B) _m- (L ₂ ) _n -DI In the formula, A reacts with an oxidized form of an aromatic primary amine developer to form (L ₁ ) _l -｛B- (L ₂ ) _m ｝ _n- DI represents a group which is cleaved, and L ₁ represents a group which is cleaved from A and then cleaves ｛B- (L ₂ ) _m ｝ _n- DI; B reacts with the oxidized developing agent (L
_{2) n} -DI represents a group which cleaves, L ₂ is _{A- (L 1) l - (} B) represents a group which cleaves DI after cleaved from _m, DI represents a development inhibitor or a precursor thereof , L, m and n each represent 0 or 1.

The reaction process in which the compound represented by the general formula (I) releases DI at the time of development is represented by, for example, the following reaction formula.

 Where A, L₁, B, L_Two, DI, l, m and n are of the general formula
Represents the same meaning as described in (I), Is
It means an oxidized developing agent.

In the general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene-type coupler residues such as acylacetanilide and malondianilide),
Magenta coupler residue (e.g., coupler residue of 5-pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type, etc.), cyan coupler residue (e.g., phenol type, naphthol type coupler residue, etc.), and colorless coupler Residues (for example, coupler residues such as indanone type and acetophenone type) are exemplified. U.S. Patent No.
4,315,070, 4,183,752, 4,174,969, 3,96
It may be a heterocyclic coupler residue described in 1,959 or 4,171,223.

When A represents a redox group, for example, hydroquinones, catechols, 1,4-naphthohydroquinones, 1,2
-Naphthohydroquinones, sulfonamidophenols, hydrazides or sulfonamidonaphthols. These groups are, for example, JP-A-61-230135,
Nos. 62-251746, 61-278852, U.S. Pat.No. 3,364,022
No. 3,379,529, 3,639,417, 4,684,604 or J. Org. Chem., 29 , 588 (1964).

Linking group represented by L ₁ and L ₂ in the general formula (I), for example, U.S. Patent No. 4,146,396, Use group cleavage reactions hemiacetal with a described in the 4,652,516 Patent, or Nos 4,698,297, U.S. Patent 4,248,962 The timing group which causes a cleavage reaction using an intramolecular nucleophilic reaction described in No. 4, a timing group which causes a cleavage reaction using an electron transfer reaction described in U.S. Pat.No. 4,409,323 or 4,421,845, U.S. Pat.No. 4,546,073 describes a group that initiates a cleavage reaction by utilizing an imino ketal hydrolysis reaction or a group that initiates a cleavage reaction by utilizing an ester hydrolysis described in German Patent Publication No. 2,626,317. Is mentioned. L ₁ and L ₂ are hetero atom contained therein, preferably an oxygen atom, each A or the sulfur atom or a nitrogen atom _{A- (L 1) l - (} B) binds to _m.

The group represented by B in the general formula (I) is A- (L ₁ ) _l
A group that becomes a redox group or a group that becomes a coupler after further cleavage, and has the same meaning as described above for A. Specifically, for example, a group represented by B in JP-A-63-6550, a group represented by COOP (B) in U.S. Pat. No. 4,438,193, or a group represented by U.S. Pat.
No. 571 includes a group represented by RED. B is preferably bonded to A- (L ₁ ) _{l at} a hetero atom, preferably an oxygen atom, a sulfur atom or a nitrogen atom contained therein.

The group represented by DI in the general formula (I) includes, for example, U.S. Patent Nos. 3,227,554, 3,384,657, 3,615,506,
3,617,291, 3,733,201, 3,933,500, 3,9
58,993, 3,961,959, 4,149,886, 4,259,43
7, 4,095,984, 4,477,563 or British Patent No.
No. 1,450,479, tetrazolylthio group, thiadiazolylthio group, oxazolylthio group, triazolylthio group, benzimidazolylthio group, benzthiazolylthio group, tetrazolylseleno group, benzoxazolylthio group, benzotriazolyl group , A triazolyl group or a benzindazolyl group.

For examples of the compound represented by the general formula (I) and the synthesis method, A, L ₁ , B, L ₂ and DI in the general formula (I)
Are shown by known patents and literature cited for explanation.

The color light-sensitive material according to the present invention has one or more blue-sensitive emulsion layers, green-sensitive emulsion layers, and red-sensitive emulsion layers on a support. The order of these layers can be arbitrarily selected as needed. Further, as a method of improving the reaching sensitivity, it is preferable that an emulsion layer having the same color sensitivity is composed of two or more emulsion layers having different sensitivities, and it is more preferable to use a method of further improving graininess as a three-layer structure. preferable.

Further, various inventions relating to the order of layer arrangement have been made in order to achieve both high sensitivity and high image quality. These techniques may be used. The invention relating to the order of layer arrangement is described in U.S. Pat.
4,184,876, 4,129,446, 4,186,016, UK Patent 1,560,965, U.S. Patent 4,186,011, 4,267,26
No. 4, No. 4,173,479, No. 4,157,917, No. 4,165,236,
It is described in British Patent No. 2,138,962, JP-A-59-177,552, UK Patent No. 2,137,372, JP-A-59-180,556, and 59-204,038.

Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity.

A reflective layer of fine silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity. This technique is described in JP-A-59-160,135.

Also, U.S. Patent No. 3,497,350 or JP-A-59-214853
As described in the above document, a method in which the color sensitivity of the emulsion layer and the color image forming coupler are appropriately combined, and this layer is provided at the position farthest from the support, can be used.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

Usually, a yellow coupler is contained in the blue-sensitive emulsion layer, a magenta coupler is contained in the green-sensitive emulsion layer, and a cyan coupler is contained in the red-sensitive emulsion layer.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020,
No. 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619, 4,351,897, EP 73,636, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
No., Research Disclosure No. 24230 (June 1984)
), JP-A-60-43659, U.S. Patent Nos. 4,500,630 and 4,540,654 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Preferred are those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767, EP 161,626A and the like.

For color couplers 1 to 4 moles of silver halide
There are 4-equivalent couplers that form a molar color and 2-equivalent couplers that develop a 1-mol color for 2 mol of silver halide. Two-equivalent couplers are preferred because of their high silver halide utilization efficiency.
There is a problem that the amplification rate of fog is also high. Therefore, in the present invention in which the increase in fog with time is reduced, a 2-equivalent coupler can be preferably used.

As the color coupler used in the present invention, a so-called high-speed reaction coupler having high coupling reactivity can be used.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No.17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
And British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
Preferred are those described in JP-A-31-188, JP-A-59-157638 and JP-A-59-170840.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
Nos. 4,310,618 and the like, multi-equivalent couplers described in European Patent No. 173,302A, and couplers which release dyes that recolor after release, RD Nos. 11449, 24241, and bleaching described in JP-A-61-201247, etc. Accelerator releasing coupler, U.S. Pat.No. 4,553,477
And the like, and the like.

Hereinafter, specific examples of the color coupler that can be used in the invention will be described, but the invention is not limited thereto.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-aluminphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl phenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate), benzoic esters (such as 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (N, N-diethyldodecaneamide, N, N-diethyllauramide), N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Aluminum phenol, aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-tert
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.). The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably 50 ° C. or more and about 160 ° C. or less of an organic solvent can be used, typical examples are ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, JP-A-63-257747
No. 62-272248, and JP-A-1-80941.
2-benzisothiazolin-3-one, n-butyl p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or fungicides such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and still more preferably 20 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured at 25 ° C. 55% relative humidity (2 days), film swell speed T _1/2
It can be measured according to a method known in the art. For example, a strometer (swelling meter) of the type described by A. Green et al. In Photographic Science and Engineering (Photogr. Sci. Eng.), Vol. 19, No. 2, pages 124-129. by using, can be measured, T _1/2 is 30 ° C. with a color developing solution, 90% of the maximum swollen film thickness reached when treated for 3 minutes 15 seconds and the saturated film thickness, film of the T _1/2 Defined as the time to reach thickness.

The film swelling speed T1 _{/ 2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 15
0-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness−film thickness) /
It can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
The development can be carried out by a usual method described in 17643, pp. 28-29, and No. 18716, 615 left column to right column.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphates, chlorides, bromides,
It generally contains a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexyl Njiamin tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N, N-trimethylenephosphonic acid, ethylenediamine -N, N, N, N-tetramethylene phosphonic acid,
Ethylenediamine-di (o-hydroxyphenylacetic acid)
And their salts can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the following aperture ratio.

That is, The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer of the color developing solution is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III) such as amino diamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate
I) Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
Nos. 53-72623, 53-95630, 53-95631, 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group described in, for example, July, 1983; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832,
Nos. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410, 2,748,430
No. 45-883
Polyamine compound described in No. 6; Other JP-A-49-42,434
Nos. 49-59,644, 53-94,927, 54-35,727,
Compounds described in JP-A Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,2
Compounds described in JP-A-90,812 and JP-A-53-95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
And acetic acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Sulfites, bisulfites, carbonyl bisulfite adducts or the sulfinic acid compounds described in EP-A-294769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring,
JP-A Nos. 62-183460 and 62-183461, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material, and a method disclosed in JP-A-62-183461.
The method of increasing the stirring effect using the rotating means of No. 83461, and furthermore, by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and making the emulsion surface turbulent, the stirring effect is further increased. And a method of increasing the circulation flow rate of the entire processing liquid. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in
It is preferable to have the photosensitive material conveying means described in JP-A-191257, JP-A-60-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath.
The effect of preventing performance deterioration of the processing liquid is high. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" (19
1986) Sankyo Publishing, Sanitary Technology Society, “Sterilization and sterilization of microorganisms,
A fungicide described in "Encyclopedia of Fungicides" (1986), "Encyclopedia of Fungicides and Antifungal Agents" (1986) edited by the Industrial Technology Association and the Japan Society of Antifungals and Fungi can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base-type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and metals described in U.S. Pat.No.3,719,492 Salt complexes and urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38, etc.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056, European Patent 210,660A2 and the like.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 A sample 101, which is a multilayer color light-sensitive material comprising the following layers, was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and the silver halide coating amount indicates the coating amount. However, for the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.

First layer: Anti-halation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.20 UV-1 0.10 UV-2 0.20 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 Second layer: Intermediate layer Fine particle silver bromide (Equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 1.00 Cpd-2 0.20 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0mol%, internal high AgI type, sphere equivalent diameter 0.7μ) Coefficient of variation of sphere equivalent diameter 14%, tetrahedral grains) Silver coating amount 0.26 Silver iodobromide emulsion (AgI 4.0mol%, internal high AgI type, equivalent sphere diameter 0.4μ, variation coefficient of equivalent sphere diameter 22% Silver coating 0.20 gelatin 1.00 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol ExS-4 0.3 × 10 ^-4 mol ExC-1 0.42 ExC-2 0.012 ExC-3 0.029 ExC-6 0.18 Fourth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent sphere diameter 1.1 µm, equivalent sphere diameter Coefficient of variation 35%, plate-like particles, / Thickness Ratio 3.0) silver coverage 0.55 Gelatin ^{0.70 ExS-1 3 × 10 -4} ExS-2 1 × 10 -4 ExS-3 0.3 × 10 -4 ExS-4 0.3 × 10 -4 ExC-6 0.08 ExC- 3 0.05 ExC-4 0.10 Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, sphere equivalent diameter 1.2 µ, sphere equivalent diameter variation coefficient 28%, Plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 0.90 Gelatin 0.60 ExS-1 2 × 10 ^-4 ExS-2 0.6 × 10 ^-4 ExS-3 0.2 × 10 ^-4 ExC-4 0.07 ExC-5 0.06 Solv -1 0.12 Solv-2 0.12 6th layer: Intermediate layer Gelatin 1.00 Cpd-4 0.009 7th layer: 1st green sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent sphere diameter) 0.7μ, sphere equivalent diameter variation coefficient 14%, tetrahedral grain) Silver coating amount 0.20 Silver iodobromide emulsion (AgI 1.0mol%, internal high AgI type, sphere equivalent diameter 0.4μ, sphere equivalent diameter variation coefficient Silver coating amount 0.10 Gelatin 1.20 ExS-5 5 × 10 ^-4 ExS-6 2 × 10 ^-4 ExS-7 1 × 10 ^-4 ExM-1 0.50 ExM-2 0.12 ExM-5 0.037 Solv-1 0.20 Solv-5 0.017 Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, Equivalent sphere diameter 1.1μ, Coefficient of variation of sphere equivalent diameter 35%, plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0.40 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 ExS-6 1.4 × 10 ^-4 ExS-7 0.7 × 10 ^-4 ExM-1 0.09 ExM-3 0.01 Solv-1 0.15 Solv-5 0.003 Ninth layer: Intermediate layer Gelatin 0.5 Tenth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (AgI. 0 molar%, internal high AgI type, sphere-corresponding diameter 1.2 microns, variation coefficient number 28 percent of the equivalent spherical diameter, the plate-like particles, diameter / thickness ratio 6.0) silver coverage of 1.00 gelatin 0.80 ExS-5 2 × 10 ^{- 4} ExS-6 0.8 × 10 ^-4 ExS-7 0.8 × 10 ^-4 ExM-4 0.04 ExM-3 0.01 ExC-4 0.005 Solv-1 0.20 Layer 11: Yellow filter layer Cpd-3 0.05 Gelatin 0.50 Solv-1 0.10 12th layer: Intermediate layer Gelatin 0.50 Cpd-2 0.10 Cpd-4 0.1 4 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent spherical diameter 0.7 μ, variation coefficient of equivalent spherical diameter 14%, tetradecahedral grain) Silver coating amount 0.10 Silver iodobromide emulsion (AgI 4.0 mol%, internal high iodine type, equivalent spherical diameter 0.4 μ, coefficient of variation of equivalent spherical diameter 22%, tetradecahedral grains) Silver coating amount 0.05 Gelatin 1.00 ExS-8 3 × 10 ^-4 ExY-1 0.53 ExY-2 0.02 Solv-1 0.15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, sphere equivalent diameter 1.0μ, sphere equivalent diameter Coefficient of variation 16%, tetrahedral particles) Silver coating amount 0.19 Gelatin 0.30 ExS-8 2 × 10 ^-4 ExY-1 0.22 Solv-1 0.07 15th layer: Intermediate layer Fine grain silver iodobromide (AgI2 mol%, uniform type, Sphere equivalent diameter 0.13μ) Silver coating amount 0.20 Gelatin 0.36 16th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, sphere equivalent diameter 1.5μ, sphere equivalent diameter Coefficient of variation 28%, plate-like particles, diameter / thickness Ratio 5.0 silver laydown 1.0 Gelatin ^{0.5 ExS-9 1.5 × 10 -4} ExY-1 0.20 Solv-1 0.07 17th layer: first protective layer Gelatin 1.80 UV-1 0.10 UV-2 0.20 Solv-1 0.01 Solv-2 0.01 18th layer: 2nd protective layer Fine particle silver bromide (sphere equivalent diameter 0.07 μ) Silver coating amount 0.18 Gelatin 0.70 Polymethyl methacrylate particles (diameter 1.5 μ) 0.20 W-1 0.02 H-1 0.40 Cpd-5 1.00 In addition to the above, B-1 is contained as a thickener, and the total applied amount of B-1 is 0.18 g / m ² . In addition, in addition to the above components, 1,2-benzisothiazolin-3-one (about 200 ppm based on gelatin) and n-butyl p-hydroxybenzoate (about 2,000
0 ppm) was added.

Sample 1 with reduced potassium ion content from Sample 101
02, 103 and 104 were created. The amount of potassium ions was reduced by the method described below. The emulsion and emulsion used to prepare Sample 101 contain B-1 and this B-1 contains a potassium ion as a counter ion. Therefore, B-1 was changed to a counter ion of sodium. Further, some compounds other than B-1, for example, sensitizing dyes and the like also contain potassium ions, so these were changed to those of sodium ions or triethylamine. Furthermore, formation of silver halide grains and emulsion
The alkali halide used for pAg adjustment was changed from a potassium salt to a sodium salt. Sample 102 with reduced potassium ion content by combining these methods
Created ~ 104. Samples 102 to 104 were prepared by intentionally changing the potassium ion content.

Samples 101-104 were analyzed for potassium ion content by atomic absorption spectroscopy. Samples to be analyzed were prepared by the method described below. 2 cm × 5 cm (10 cm ² ) of each film was cut out and wet-ashed with 5 ml of H ₂ SO ₄ and 3.5 ml of HNO ₃ , and H ₂ O was added to make 10 ml. In addition, H ₂ SO ₄ and HNO ₃
The same operation was carried out using only 5 samples, and a known amount of potassium ion was added thereto to prepare a calibration curve solution. The measurement was performed in a flame light mode using a Hitachi Zeeman type atomic absorption spectrometer.

Table 1 shows the potassium ion content of Samples 101 to 104 in terms of the weight per unit area of the samples.

D-30 (ExC) contained in the third layer of Samples 101 to 104
-2) was replaced with equimolar amounts of D-52 and D-33,
5-108 and 109-112 were created respectively.

Samples 101 to 112 were stored under the storage conditions shown in Table 2, then exposed to a wedge according to a conventional method for measuring sensitometric performance (sensitivity, fog) and granularity, and processed by the processing steps described below. The treated samples were subjected to sensitometry and granularity measurements with blue, green and red light, respectively.

Specific photographic sensitivity ... blue, green, respectively represent the exposure amount corresponding to 0.15 higher concentrations relative to the minimum density of the characteristic curve of each measured red light lux · second H _B, H _G, and H _R, further H _B and
The larger value (lower sensitivity) of H _R is defined as H _S.
At this time, the specific photographic sensitivity S is calculated by the following equation.

Therefore, the larger the value of the specific photographic sensitivity S, the higher the sensitivity.

Fog: The minimum density of the characteristic curve obtained by sensitometry. The higher the value, the higher the fog, which is not preferable.

Granularity (RMS): The standard deviation of the density value fluctuation that occurs when a dye image having a minimum dye image density of +1.2 is processed by a microdensitometer with a circular scanning aperture of 48μ. Is not preferred.

Table 3 shows the measurement results for the samples 101 to 112. For fog and granularity (RMS), data obtained for red light is shown. The granularity (RMS) is shown as a relative value with respect to the storage condition (A) of the sample 101 as 100.

 Processing method Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 6 minutes 30 seconds 38 ° C Rinse 2 minutes 10 seconds 24 ° C Fixed 4 minutes 20 seconds 38 ° C Rinse (1) 1 minute 05 seconds 24 ° C Rinse (2) 2 minutes 10 seconds 24 ° C Stabilization 1 minute 05 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C Next, the composition of the processing solution is described.

(Color developing solution) (unit g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Add water 1.0l pH 10.05 (Bleaching solution) (g) Ferric ethylenediaminetetraacetate sodium trihydrate 100.0 Ethylenediaminetetraacetic acid Thorium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5ml Add water 1.0l pH 6.0 (fixer) (unit g) Sodium sodium ethylenediaminetetraacetate 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Thio Ammonium sulfate aqueous solution (70%) Add 170.0ml water and add 1.0l pH 6.7 (stabilizer) ( Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Sodium ethylenediaminetetraacetate 0.05 Add water 1.0l pH 5.0-8.0 As is clear from Table 3, the sample of the present invention has the same or slightly lower sensitivity and almost the same granularity under the storage condition (A) as the comparative sample, but the storage condition (B)
It can be seen that the sample of the present invention has a small increase in fog, a relatively small deterioration in graininess, and a small degree of sensitivity decrease, as compared with the comparative sample.

Further, as shown in Table 1, the amount of potassium ions contained in the sample was largest in sample 101, and in samples 102, 103, 1
Since the number decreases in the order of 04, it can be seen from the results in Table 3 that the smaller the amount of potassium ions contained, the smaller the performance deterioration with time. This is the same for the samples 105 to 108 or the samples 109 to 112.

Further, from Table 3, it can be seen that the degree of aging is different depending on the development inhibitor releasing compound used, which is related to the diffusibility of the development inhibitor.

Example 2 A sample 201 as a multilayer color photographic material comprising the following layers was prepared on an undercoated cellulose triacetate film support.

The number corresponding to each component (the composition of the photosensitive layer) indicates the coating amount in g / m ^2,
For silver halide, the coating amount is expressed in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.

First layer: anti-halation layer Black colloidal silver 0.20 Gelatin 1.00 UV-1 0.10 UV-2 0.10 UV-3 0.10 UV-4 0.10 Solv-1 0.20 Solv-2 0.10 ExM-1 0.02 Second layer: Intermediate layer Gelatin: 1.00 Solv-1 ... 0.01 Third layer: First red-sensitive emulsion layer Monodispersed silver iodobromide emulsion (AgI: 8 mol%, average particle size: 1.0 μm): 0.90 Monodispersed iodobromide Silver emulsion (AgI3mol%, average particle size 0.5μ) ... 0.30 ExS-1 ... 7 x ^10-5 ExS-2 ... 1.4 x ^10-4 ExC-1 ... 0.30 ExC-2 ... 0.20 ExC-3 ... 0.02 ExC -4 ... 0.01 Solv-3 ... 0.03 Solv-4 ... 0.03 Fourth layer: Intermediate layer Gelatin ... 1.00 Cpd-1 ... 0.10 Fifth layer: First green-sensitive emulsion layer Monodispersed silver iodobromide emulsion (AgI8 mol%) 1.00 monodispersed silver iodobromide emulsion (3 mol% AgI, average particle size 0.5 μm) 0.30 gelatin 0.80 ExS-3 2 × 10 ^-4 ExS-4 1 × 10 ^{− 4 ExS-5 ... 1 × 10} -4 ExS-6 ... 1 × 10 -4 ExS-7 ... ^{× 10 -4 ExM-1 ... 0.10} ExM-2 ... 0.70 Solv-3 ... 0.10 Sixth layer: intermediate layer Gelatin ... 1.00 Cpd-1 ... 0.10 Seventh Layer: First Blue-sensitive emulsion layer Monodisperse silver iodobromide emulsion (AgI 8 mol%, average particle size 1.0μ) ... 0.80 Gelatin ... 1.00 ExS-8 ... 2 x 10 ^-4 ExS-9 ... 2 x 10 ^-4 ExY-1 ... 1.10 8th layer: Intermediate layer Gelatin ... 1.00 Cpd -1 ... 0.10 Solv-5 ... 0.05 9th layer: 2nd red-sensitive emulsion layer Monodispersed silver iodobromide emulsion (6 mol% AgI, average grain size 2.5μ) ... 1.90 Monodispersed silver iodobromide emulsion (AgI8 0.50 Monodispersed silver iodobromide emulsion (AgI3mol%, average particle size 0.4μ) ... 0.20 Gelatin ... 1.20 ExS-1 ... 2 x ^10-5 ExS-2 ... 7x 10 ^-5 ExC-2 ... 0.20 ExC-3 ... 0.10 Solv-4 ... 0.20 10th layer: Intermediate layer Gelatin ... 1.00 Cpd-1 ... 0.10 11th layer: Second green-sensitive emulsion layer Monodisperse silver iodobromide emulsion ( AgI 6 mol%, average particle size 2.5 μ)… 1.50 monodispersed silver iodobromide emulsion (AgI 8 mol% 0.30 Gelatin 1.00 ExS-3 2 × 10 ^-4 ExM-1 0.10 ExM-2 0.20 Solv-1 0.40 12th layer: Intermediate layer Fine grain silver bromide emulsion (average grain) Diameter 0.07μ) ... 0.20 Gelatin ... 1.20 Cpd-1 ... 0.10 13th layer: 2nd blue-sensitive emulsion layer Monodisperse silver iodobromide emulsion (AgI 6% by mole, average particle size 2.5μ) ... 1.40 Monodisperse iodoodor Silver iodide emulsion (AgI 8 mol%, average grain size 1.0 μ)… 0.30 Monodisperse silver iodobromide emulsion (AgI 3 mol%, average grain size 0.4 μ)… 0.20 Fine grain silver iodobromide emulsion (average grain size 0. 09μ)… 0.20 Gelatin… 1.20 ExS-8… 1 × 10 ^-4 ExS-9… 3 × 10 ^-4 ExY-1… 0.30 Solv-1… 0.06 14th layer: 1st protective layer UV-1… 0.05 UV- 2… 0.05 UV-3… 0.05 UV-4… 0.05 UV-5… 0.02 Gelatin… 0.60 Solv-4… 0.10 15th layer: Second protective layer Gelatin… 0.50 Polymethyl methacrylate particles (1.5μ in diameter)… 0.20 Is a thickener in addition to the above ingredients It is contained in B-1 Te, the total amount of the coating weight B-1 is 0.07 g / m ^2. Further, a surfactant W-1 was added as a coating aid,
Further, formalin scavenger was added. Further, in addition to the above components, 1,2-benzisothiazoline-
3-one (about 200 ppm based on gelatin) and 2-phenoxyethanol (about 2,000 ppm) were added.

Sample 2 with reduced potassium ion content from Sample 201
02 was created. The reduction in the amount of potassium ions is described in Example 1.
The procedure was performed in the same manner as described above. Further, only the coating amounts of the silver iodobromide emulsions of the third layer, the fifth layer, the seventh layer, the ninth layer, the eleventh layer, and the thirteenth layer with respect to the sample 202 were changed as shown in Table 4 to obtain a sample 20.
I made 3,204.

The potassium ion content of the samples 201 to 204 thus obtained was measured in the same manner as in Example 1. This result is the fifth
It is shown in the table.

Samples 201 to 204 were stored under the storage conditions shown in Table 2 and then exposed to a wedge according to a standard method for measuring sensitometric performance and granularity, and processed in the same processing steps as in Example 1. The treated samples were subjected to sensitometry and granularity measurements with blue, green and red light, respectively. The measurement results at this time are shown in Table 6. As for fog and granularity, data obtained for red light are shown, but almost the same results were obtained when measured with blue light and green light. The granularity is shown as a relative value with respect to the storage condition (A) of the sample 201 as 100.

From Table 6, it can be seen that in this system, the sample 202 in which only the amount of potassium ions was reduced did not significantly improve the performance deterioration such as an increase in fog over time with respect to the sample 201. On the other hand, the samples 203 and 204 of the present invention are slightly inferior in sensitivity and granularity under the storage condition (A) as compared with the sample 201, but this difference does not cause much problem in practice. However, under the storage condition (B), it can be seen that Samples 203 and 204 of the present invention are clearly superior to Samples 201 and 202 in all of sensitivity, granularity, and fog. That is, according to the present invention, deterioration of photographic performance over time is improved.

Example 3 A sample 301, which is a multilayer color light-sensitive material comprising the following layers, was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and the silver halide coating amount indicates the coating amount. However, for the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.

First layer: Anti-halation layer Black colloidal silver ... 0.18 Gelatin ... 0.40 Second layer: Intermediate layer Gelatin ... 1.04 UV-1 ... 0.06 UV-2 ... 0.08 UV-3 ... 0.10 Solv-1 ... 0.10 Solv-2 ... 0.02 ExM -1 ... 0.07 ExC-1 ... 0.02 Cpd-1 ... 0.18 Cpd-2 ... 0.002 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 4.3 mol%, middle high AgI type, equivalent sphere diameter) 0.45μ, sphere equivalent diameter variation coefficient 27%, diameter / thickness ratio 1.0)… 0.25 silver iodobromide emulsion (AgI 8.7mol%, middle high AgI type, sphere equivalent diameter 0.7μ, sphere equivalent diameter Coefficient of variation 14%, diameter / thickness ratio 1.0) ... 0.25 Gelatin ... 0.87 ExC-2 ... 0.34 ExC-3 ... 0.02 ExS-1 ... 3.1 x ^10-4 ExS-2 ... 6.9 x ^10-5 ExS-3 ... 1.8 × 10 ^-5 fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 30%, diameter / thickness ratio 2.0) ... 1.00 Gelatin ... 1.30 ExC-1 ... 0.05 ExC-2 0.40 ExC-3 ... 0.02 ExS- 1 ... 2.3 × 10 -4 ExS-2 ... 5.1 × 10 -5 ExS-3 ... 1.4 × 10 -5 Fifth Layer: Third Red-sensitive emulsion layer silver iodobromide emulsion (AgI10 Mol%, internal high AgI type, sphere equivalent diameter 1.05μ, coefficient of variation of sphere equivalent diameter 35%, diameter / thickness ratio 2.0) ... 1.60 gelatin ... 1.63 ExC-1 ... 0.01 ExC-2 ... 0.10 ExC-4 ... 0.08 ExS-1… 2.4 × 10 ^-4 ExS-2… 5.4 × 10 ^-5 ExS-3… 1.4 × 10 ^-5 Solv-1… 0.22 Solv-1… 0.10 6th layer: Intermediate layer Gelatin… 0.80 Cpd-3 ... 0.04 Solv-1 ... 0.02 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (AgI 4.3%, middle high AgI type, equivalent spherical diameter 0.45μ, coefficient of variation of equivalent spherical diameter 27%) 0.15 silver iodobromide emulsion (AgI 8.7 mol%, middle high AgI type, sphere equivalent diameter 0.7 μ, sphere equivalent diameter variation coefficient 14%, diameter / thickness ratio 1.0) )… 0.15 Gelatin… 0.63 ExM-1… 0.02 ExM-2… 0.26 ExM-3… 0.03 ExY-1… 0.03 ExS-4… 3.8 × 1 0 ^-4 ExS-5 ... 3.0 x 10 ^-5 ExS-6 ... 1.0 x 10 ^-4 Solv-1 ... 0.10 Solv-3 ... 0.01 Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%) , Internal high AgI type, equivalent spherical diameter 0.75μ, coefficient of variation of equivalent spherical diameter 30%, diameter / thickness ratio 2.0)… 0.45 Gelatin… 0.50 ExM-2… 0.09 ExM-3… 0.03 ExY-4… 0.02 ExS -4 2.6 × 10 ^-4 ExS-5 2.1 × 10 ^-5 ExS-6 7.0 × 10 ^-5 Solv-1 0.16 Solv-3 0.01 Ninth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%) , Internal high AgI type, sphere equivalent diameter 1.05μ, coefficient of variation of sphere equivalent diameter 35%, diameter thickness ratio 3.0) ... 1.20 gelatin ... 1.54 ExM-1 ... 0.03 ExM-4 ... 0.10 ExM-5 ... 0.02 ExS-4 3.0 × 10 ^-4 ExS-5 3.5 × 10 ^-5 ExS-6 8.0 × 10 ^-5 Solv-1 0.25 Solv-2 0.10 10th layer: Yellow filter layer Yellow colloidal silver… 0.05 Gelatin… 0.95 Cpd-3… 0.08 Solv -1 0.03 11th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 4.3 mol%, medium AgI type, sphere equivalent diameter 0.45μ, variation coefficient of sphere equivalent diameter 14%, diameter / thickness ratio 1.0) ... 0.08 silver iodobromide emulsion (AgI 4.3 mol%, middle high AgI type, sphere equivalent diameter 0.70) μ, variation coefficient of sphere equivalent diameter 14%, diameter / thickness ratio 1.0)… 0.07 Silver iodobromide emulsion (AgI 4.3 mol%, middle high AgI type, sphere equivalent diameter 0.25μ, sphere equivalent diameter variation Coefficient 28%, diameter / thickness ratio 1.0) ... 0.07 Gelatin ... 1.10 ExY-1 ... 0.04 ExY-2 ... 0.72 ExS-7 3.5 x ^10-4 Solv-1 0.28 12th layer: 2nd blue-sensitive emulsion layer Silver bromide emulsion (AgI 14 mol%, internal high AgI type, equivalent sphere diameter 0.75 μ, coefficient of variation of equivalent sphere diameter 25%, diameter / thickness ratio 2.0) 0.45 Gelatin 0.78 ExY-2 0.15 ExC-3 ... 0.007 ExS-7 2.1 × 10 ^-4 Solv-1 0.05 13th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14 mol%, internal high AgI type, equivalent sphere diameter 1.30μ, equivalent sphere diameter) Coefficient of variation 25%, diameter / thickness ratio 3.0)… 0.77 Gelatin… 0.69 Ex Y-1 ... 0.20 ExS-7 2.2 × 10 ^-4 Solv-1 0.07 14th layer: 1st protective layer Fine grain silver iodobromide (AgI 1 mol%, equivalent sphere diameter 0.07μ)… 0.50 Gelatin… 1.00 UV-4… 0.11 UV-5 ... 0.17 Solv-1 0.05 15th layer: 2nd protective layer Polymethyl acrylate particles (diameter about 1.5μ) ... 0.54 Gelatin ... 1.20 Cpd-4 ... 0.20 Solv-1: tricresyl phosphate Solv-2: didibutyl phthalate Each layer contains, in addition to the above components, a gelatin hardener H-1.
And a surfactant were added. In addition, thickener B-1 was added to each layer.
And the coating amount of B-1 is 0.17 g / m ² .

Sample 302 with reduced potassium ion content of sample 301
Created ~ 304. The potassium ion content was reduced in the same manner as in Example 1. The potassium ion content of samples 301 to 304 was measured in the same manner as in Example 1,
The results are shown in Table 7.

The development inhibitor-releasing compound D-45 (ExC-3) contained in the fourth layer of Samples 301 to 304 was equimolarly mixed with D-52 and D-2.
Samples 305 to 308 and 309 to 312 were prepared by substituting 6 for each.

After storing the samples 301 to 312 under the storage conditions shown in Table 2, sensitometric performance and granularity were measured in the same manner as in Example 1. Table 8 shows the measurement results at this time. For fog and granularity, data obtained for red light is shown. The granularity is shown as a relative value with respect to the storage condition (A) of the sample 301 as 100.

As is clear from Table 8, the sample of the present invention has the same sensitivity and the same granularity under the storage condition (A) as that of the sample 301, but under the storage condition (B), due to the reduction of potassium ion amount, It can be seen that the deterioration of the photographic performance is improved and the performance is improved.

It can also be seen that the degree of improvement in the aging performance differs depending on the development inhibitor-releasing compound used, and is related to the diffusivity of the development inhibitor.

Example 4 A sample 401, which is a multilayer color light-sensitive material having the following compositions, was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The coating amount is g / g for silver halide and colloidal silver.
The amount of silver expressed in m ² units, the amount expressed in g / m ² for couplers, additives and gelatin, and the number of moles per mole of silver halide in the same layer for sensitizing dyes Indicated by

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.2 Gelatin 2.2 UV-1 0.1 UV-2 0.2 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 Second layer: Intermediate layer Fine particle silver bromide (Equivalent sphere diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.0 ExC-4 0.03 Cpd-2 0.2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter) 1.0 μm, Coefficient of variation of sphere equivalent diameter 25%, tabular grain, diameter / thickness ratio 3.0) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter 0.4 μm, equivalent to sphere) Coefficient of diameter variation 22%, tetradecahedral particles Silver coating amount 0.33 Gelatin 1.0 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol ExC-1 0.40 ExC -2 0.11 ExC-3 0.009 ExC-4 0.023 Solv-1 0.24 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, sphere equivalent diameter Variator 25%, tabular grain, diameter / thickness ratio 3.0) silver coverage 0.55 Gelatin 0.7 ExS-1 3 × 10 ^-4 mol ExS-2 1 × 10 ^-4 mol ExS-3 0.3 × 10 ^-4 mol ExC-1 0.10 ExC-2 0.05 ExC-4 0.025 Solv-1 0.20 Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, equivalent spherical diameter of 1.4 μm, coefficient of variation of equivalent spherical diameter) 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.29 Gelatin 0.6 ExS-1 2 × 10 ^-4 mol ExS-2 0.6 × 10 ^-4 mol ExS-3 0.2 × 10 ^-4 mol ExC-2 0.08 ExC-4 0.01 ExC-5 0.06 Solv-1 0.12 Solv-2 0.12 Sixth layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 Solv-1 0.1 Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 Mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter / thickness ratio 3.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal height AgI type, equivalent sphere diameter 0.7μm, variation of equivalent sphere diameter Number 38%, tabular grain, diameter / thickness ratio 2.0) silver coverage 1.0 Gelatin 1.2 ExS-5 5 × 10 ^-4 mol ExS-6 2 × 10 ^-4 mol ExS-7 1 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 0.03 Solv-1 0.2 Solv-5 0.03 Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high iodine type, equivalent spherical diameter 1.0 μm, spherical Coefficient of variation of equivalent diameter 25%, plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0.47 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 mol ExS-6 1.4 × 10 ^-4 mol ExS-7 0.7 × 10 ^-4 mol Mol ExM-1 0.12 ExM-3 0.01 Solv-1 0.15 Solv-5 0.03 9th layer: intermediate layer Gelatin 0.5 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type) Sphere equivalent diameter 1.4μm, sphere equivalent diameter variation coefficient 28%, plate-like particle, diameter / thickness ratio 6.0) silver coating amount 1.3 gelatin 0.8 ExS-5 2 × 10 ^-4 mol ExS-6 0.8 × 10 ^-4 mol ExS-7 0.8 × 10 ^-4 mol ExM-3 0.01 ExM-4 0.04 ExC-4 0.005 Cpd-5 0.01 Solv-1 0.2 11th layer: yellow filter layer Cpd-3 0.05 gelatin 0.5 Solv-1 0.1 12th layer: middle layer Gelatin 0.5 Cpd-2 0.1 13th layer: first blue-sensitive emulsion Layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent spherical diameter 0.7 μm, coefficient of variation of equivalent spherical diameter 14%, tetradecahedral grains) Silver coating amount 0.1 Silver iodobromide emulsion (AgI 4.0 Mol%, internal high AgI type, equivalent sphere diameter 0.4 μm, variation coefficient of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.05 Gelatin 1.0 ExS-8 3 × 10 ^-4 mol ExY-1 0.6 ExY- 2 0.02 Solv-1 0.15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent spherical diameter 1.0 μm, coefficient of variation of equivalent spherical diameter 16%, 14 faces Silver coating amount 0.19 Gelatin 0.3 ExS-8 2 × 10 ^-4 mol ExY-1 0.22 Solv-1 0.07 15th layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0.13) μm) silver Cloth 0.2 Gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, equivalent spherical diameter 1.7 μm, coefficient of variation of equivalent spherical diameter 28%, tabular grains, Diameter / thickness ratio 5.0) Silver coating amount 1.4 Gelatin 0.5 ExS-9 1.5 × 10 ^-4 mol ExY-1 0.2 Solv-1 0.07 17th layer: First protective layer Gelatin 1.8 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 18th layer: 2nd protective layer Fine particle silver chloride (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.7 Polymethyl methacrylate particles (diameter 1.5 μm) 0.2 W-1 0.02 H-1 0.4 Cpd-6 1.0 In addition to the above, B-1 (total 0.20 g / m ² ), 1,2-benzisothiazolin-3-one (about 200 ppm based on gelatin), and n-butyl p-hydroxybenzoate (each) About 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm).

Sample 4 with reduced potassium ion content from Sample 401
02 to 404 were created. The amount of potassium ions was reduced in the same manner as in Example 1. Table 9 shows the potassium ion content of the samples 401 to 404 measured by the same method as in Example 1.

D-30 (ExC-) contained in the third layer of samples 401 to 404
Samples 405 to 4 were obtained by substituting 3) with equimolar D-52 and D-45.
08, 409-412 were created respectively.

After storing the samples 401 to 412 under the same conditions as in Example 1, the sensitivity, fog, and granularity were measured in the same manner as in Example 1. The specific photographic sensitivity of the sample 401 under the storage condition (A) was 1640, and the samples 402 to 412 had almost the same sensitivity. The degree of deterioration of the photographic performance under the storage condition (B) with respect to the condition (A) is smaller for a sample having a lower potassium ion content,
When the potassium ion content was the same, the sample rewritten with D-45 was the smallest and the sample replaced with D-52 was the largest. That is, similarly to the result in Example 1, the sample having a smaller amount of potassium ion contained had smaller performance deterioration with the lapse of time, and the degree of deterioration with the lapse of time also varied depending on the development inhibitor releasing compound used, and the diffusibility of the development inhibitor was larger. It was found that the performance degradation with time was smaller for the sample using the sample.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-836 (JP, A) JP-B-6-70710 (JP, B2) JP-B-6-70711 (JP, B2) US Patent 4,952,485 (US) , A) U.S. Pat. No. 3,519,426 (US, A) European Patent Publication 328042 (EP, A2) Photographic Industry November 1986, pp. 92-96.

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the total amount of potassium ions contained in the light-sensitive material is 20 mg / m ² or less; and the total amount of all of the silver contained in the photosensitive material is 3.0~9.0g / m ^2, at least one layer reacts with an oxidation product of a color developing agent development inhibitor or a precursor of a silver halide emulsion layer The compound that is cleaved after reacting with the compound to be released and / or the oxidized form of the color developing agent further contains a compound that cleaves the development inhibitor or its precursor by reacting with the oxidized form of the color developing agent, and the specific photographic sensitivity is reduced. A silver halide color photographic light-sensitive material characterized by having a particle size of 320 or more.