JPH05341450A - Silver halide photographic product - Google Patents

Abstract

PURPOSE:To preserve a photosensitive material having high sensitivity and excellent graininess in a transparent case which hardly changes the sensitivity or fog during storage after production and before use. CONSTITUTION:This silver halide photographic product consists essentially of a silver halide photosensitive material obtd. by forming at least one silver halide emulsion layer contg. a thiocyanate and a silver halide emulsion chemically sensitized in the presence of a gold sensitizer and a selenium sensitizer on a base, a light shielding vessel 2 contg. the photosensitive material and a hermetically sealing transparent vessel 5 for housing the light shielding vessel 2. The photosensitive material is contained in the vessel 2 so that part of the material 2 is positioned at the outside of the vessel 2 and gas is allowed to circulate between the inside and outside of the vessel 2. This photographic product has a gaseous hydrogen cyanide scavenger at a certain position in the hermetically sealed vessel 5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic product, and more specifically, it has high sensitivity and excellent graininess, and the fluctuations in sensitivity and fog during the storage period before the use of the photographic material after its production are used. It relates to a silver halide photographic product held in a low, light-transmissive case.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic materials are photosensitive. Therefore, it is usually shielded from light and stored before being photographed. However, there are cases where light-shielding is not sufficient for a portion which is not photographed due to design restrictions of photographic products. For example, in the case of the color negative film of the 135 format, if the case for storing the film cartridge is transparent, the inside cartridge can be easily seen and confirmed, and the transparent case has an advantage that it can be reused as an accessory case.

[0003]

Recently, however, a surprising phenomenon has been discovered in which the performance of the film varies depending on the brightness of the place where the product is stored for a long time on the shelves of the store. .. Analysis of this phenomenon revealed that light hits the drawer of the film through the paper box that houses the film case, and a certain type of gas is generated, and this gas diffuses to the part that is blocked by the light. It turns out that the performance is changing. Such a phenomenon has never been known in the art. For the purpose of analyzing this gas, the film was forcibly irradiated with intense light and the generated gas was collected, and it was found that hydrogen cyanide gas was contained.

If the silver halide is altered by the influence of hydrogen cyanide gas and the photographic performance is changed, the scavenger of hydrogen cyanide gas should be effective.

As a scavenger for hydrogen cyanide gas, it is disclosed in JP-A-3-505263 that compounds of palladium, gold and platinum are effective. Here, it is described that fogging caused by hydrogen cyanide gas generated from carbon black is prevented by including a hydrogen cyanide scavenger at a position where it can be blocked from the photosensitive emulsion.

It is also stated that it is preferable that the addition position of the scavenger is closer to the carbon black which is the generation source.

However, there is no description suggesting that hydrogen cyanide gas is generated when the light-sensitive material is irradiated with light.

There is no description suggesting that the gas generated from the light-irradiated portion affects the photographic properties of the light-shielded portion.

Further, there is no description that the thiocyanic acid compound contained in the light-sensitive material causes gas generation.

For example, as disclosed in US Pat. Nos. 2,566,245 and 2,566,263, it is widely known to add a Pd compound to a silver halide photographic light-sensitive material. This is a known technique. Actually, Pd is contained in the emulsion layer or the intermediate layer of the silver halide color photographic material.
Is widely practiced, eg 1988
Eastman Kodak Company's Rochuster Factory in New York, USA, valid for December, 2012
R-G100 Brownie film (EMUL.NO.2
4 031 13) has a Pd of about 3 × 10 ^-5.
It is contained in a black light-shielding paper containing about 8% of carbon black (about 0.7 g per one), and this film is hydrogen cyanide gas generated by light irradiation. Is believed to have had no effect.

Further, it is predicted that this Pd is effective against fog that may occur when the same light-sensitive material is commercialized in a film format having a design having a portion to be irradiated with light as in the present invention. Is impossible.

In the present invention, it is believed that the following reactions occur in the light-irradiated portion to generate hydrogen cyanide gas.

AgBr (+ hν; light irradiation) → 2Ag + Br ₂ (printout) 2AgSCN + Br ₂ → 2AgBr + (SCN) ₂ (SCN) ₂ hydrolysis → HCN From this reaction formula, it is found that a scavenger of halogen gas is also effective. Will.

In the case of a silver halide emulsion having a high photosensitivity, it is expected that the amount of bromine gas generated during printout will increase and the amount of hydrogen cyanide gas will also increase.

Further, it is expected that the generation of hydrogen cyanide gas will increase when the humidity in the photographic product is high.

On the other hand, the silver halide emulsion used in the silver halide photographic light-sensitive material is usually chemically sensitized with various chemical substances in order to obtain desired sensitivity, gradation and the like. As a typical method thereof, sulfur sensitization, selenium sensitization, noble metal sensitization such as gold, reduction sensitization, and a combination thereof are used.
Various sensitization methods are known.

In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, and rapid processing for accelerating the progress of development, and various improvements of the above-mentioned sensitization method have been made. It has been done.

Among the above sensitizing methods, the selenium sensitizing method is described in, for example, US Pat. Nos. 1,574,944 and 16;
No. 02592, No. 1623499, No. 32974.
No. 46, No. 3297447, No. 3320069
No. 3,408,196, No. 3408197, No. 3442653, No. 3420670, No. 35.
No. 91385, French Patent No. 2693038, No. 2093209, Japanese Patent Publication No. 52-34491, No. 52.
-34492, 53-295, and 57-2209.
No. 0, JP-A-59-180536 and JP-A-59-1853.
30, No. 59-181337, No. 59-18733.
No. 8, No. 59-192241, No. 60-150046.
No. 60, No. 60-151637, No. 61-246738.
No., British Patent Nos. 255,846 and 861984,
And H .; E. Spencer et al., Journal of
Photographic Science Magazine, 31
Vol. 158-169 (1983). In general, selenium sensitization has a greater sensitizing effect than sulfur sensitization which is usually performed in the art, but it tends to cause large fog and tend to be softened. Many of the known patents mentioned above remedy these drawbacks, but still give unsatisfactory results.

When gold sensitization is used in combination with selenium sensitization or sulfur-selenium sensitization, greater sensitivity sensitization can be obtained as compared with gold-sulfur sensitization, but the photographic performance due to the influence of hydrogen cyanide gas is increased. Deterioration is significantly worse than gold-sulfur sensitization and is a major problem.

The deterioration of photographic performance due to hydrogen cyanide gas is, as described in JP-A-3-505263, a halogenation sensitized by gold-sulfur or gold- (sulfur) -selenium by hydrogen cyanide gas. It is considered that this is caused by the fact that silver sulfide or silver selenide fog center, which has a high fog activity, remains due to the migration of gold from the silver emulsion.

It has already been known that the fog activity of the silver selenide fog center is significantly higher than that of the silver sulfide fog center. As described above, the deterioration of the photographic performance due to the hydrogen cyanide gas is higher than that of the gold-sulfur sensitization. It is believed that this is the reason for the marked deterioration in the gold- (sulfur) -selenium sensitized emulsion.

An object of the present invention is to provide a silver halide photographic product having high sensitivity and excellent graininess. Another object of the present invention is to provide a silver halide photographic product which is held in a light-transmissive case with little fluctuation in sensitivity and fog during the storage time after the production of the light-sensitive material until it is used. ..

[0023]

The object of the present invention can be achieved by the following. (1) Halogen in which at least one silver halide emulsion layer containing a silver halide emulsion and a thiocyanate chemically sensitized in the presence of a gold sensitizer and a selenium sensitizer is provided on a support. A silver halide light-sensitive material, a light-shielding container containing the light-sensitive material, and a light-transmissive sealed container containing the light-shielding container. The light-sensitive material is incorporated so that a part thereof is located outside the light-shielding container. And a silver halide photographic product having a structure in which a gas can flow between the inside and the outside of the light-shielding container, characterized by having a hydrogen cyanide gas scavenger at any position in the sealed container. Silver photographic product. (2) The silver halide photographic product according to (1) above, which has a halogen gas scavenger at any position in the sealed container. (3) The silver halide photographic product as described in (1) or (2) above, wherein a hydrogen cyanide gas or a halogen gas scavenger is present in the photographic light-sensitive material. (4) The above (1), wherein the hydrogen cyanide gas scavenger is an inorganic or organic compound of palladium (II or IV)
Halogenated photographic product as described. (5) The halogenated photographic product as described in (1) or (2) above, wherein the relative humidity in the sealed container is 55% or more at 25 ° C. (6) The above (1), wherein the photographic light-sensitive material is a color photographic material.
~ The halogenated photographic product according to (5). (7) 1 per mol of thiocyanate contained in the part which can be irradiated with the hydrogen cyanide gas scavenger.
The halogenated photographic product according to the above (1) or (3) to (6), which is / 10 mol or more. (8) 1 / mole of thiocyanate contained in a portion of the hydrogen cyanide gas scavenger that can be irradiated with light.
The halogenated photographic product according to the above (1) or (3) to (6), which is 2 mol or more.

The present invention will be described in detail below.

The silver halide emulsion used in the present invention is gold.
Selenium is sensitized.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-134.
89, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-229
It is preferable to use the compounds described in No. 300. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides,
Examples include colloidal metal selenium.

Particularly preferred unstable selenium compounds are shown below.

I. Colloidal metal selenium II. Organic selenium compound (selenium atom double-bonded to carbon atom of organic compound by covalent bond) a. Isoselenocyanates Aliphatic isoselenocyanates such as allyl isoselenocyanate b. Selenoureas (including enol type) For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetraoctyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N ,
Aliphatic selenoureas such as N-dimethyl, diethyl and dimethyl; aromatic selenoureas having one or more aromatic groups such as phenyl and tolyl; heterocycles having heterocyclic groups such as pyridyl and benzothiazolyl Formula selenourea c. Selenoketones, for example, selenoacetone, selenoacetophenone, selenoketone having an alkyl group bonded to> C = Se, selenobenzophenone d. Selenoamides For example, selenoacetamide e. Selenocarboxylic acids and esters For example, 2-selenopropionic acid, 3-selenobutyric acid, methyl
3-Serenobuchirate III. Other a. Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b. Selenophosphates, for example, tri-p-tolylselenophosphate, tri-n-
The preferred types of butylselenophosphate labile selenium compounds are described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and play no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

As the non-labile selenium compound used in the present invention, Japanese Patent Publication Nos. 46-4553 and 52-34 are available.
The compounds described in JP-B No. 492 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also useful.

Of these selenium compounds, the following general formulas (I) and (II) are preferable.

General formula (I)

[0033]

[Chemical 1] In the formula, Z ₁ and Z ₂ may be the same or different, and are each an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl), an aralkyl group. (Eg, benzyl, phenethyl), an aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), a heterocyclic group (eg, pyridyl group, Thienyl group, furyl group, imidazolyl group), -N
It represents R ₁ (R ₂ ), —OR ₃ or —SR ₄ .

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ .

However, R ₁ and R ₂ are each a hydrogen atom or an acyl group (eg, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl,
4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl) may be used.

In the general formula (I), preferably Z ₁ represents an alkyl group, an aryl group or --NR ₁ (R ₂ ) and Z ₂
Represents -NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R
₆ may be the same or different, a hydrogen atom,
It represents an alkyl group, an aryl group, or an acyl group.

In the general formula (I), more preferably N, N-
Dialkylselenourea, N, N, N'-trialkyl-
N'-acyl selenoureas, tetraalkyl selenoureas,
Represents N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

General formula (II)

[0039]

[Chemical 2] In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group or -OR.
_{7, -NR 8 (R 9)} , - SR 10, -SeR 11, X, represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula (II), Z ₃ , Z ₄ ,
The aliphatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aralkyl group (for example, methyl,
Ethyl, n-propyl, isopropyl, t-butyl, n
-Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula (II), Z ₃ , Z ₄ ,
The aromatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3
-Sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (II), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3-10 membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (eg, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group).

In the general formula (II), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom or a bromine atom. Or represents an iodine atom.

In the general formula (II), preferably Z ₃ , Z ₄ or Z ₅ represents an aliphatic group, an aromatic group or -OR ₇ ,
R ₇ represents an aliphatic group or an aromatic group.

In the general formula (II), trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate is more preferable.

Specific examples ("Chemical Formula 3" to "Chemical Formula 10") of the compounds represented by the general formulas (I) and (II) are shown below.
The present invention is not limited to this.

[0048]

[Chemical 3]

[0049]

[Chemical 4]

[0050]

[Chemical 5]

[0051]

[Chemical 6]

[0052]

[Chemical 7]

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10] Regarding the selenium sensitization method, for example, US Pat.
No. 44, No. 1602592, No. 1623499
No. 3,297,446, No. 3297447, No. 33320069, No. 3408196, and No. 34.
No. 08197, No. 3442653, No. 34206
70, 359.1385, French Patent 269.
No. 3038, No. 2093209, Japanese Patent Publication No. 52-34
No. 491, No. 52-34492, No. 53-295,
57-22090, JP-A-59-180536,
59-185330, 59-181337, 59-187338, 59-192241 and 6
0-150046, 60-151637, 61
-246738, JP-A-3-42221, Japanese Patent Application No. 1-
287380, 1-250950, 1-254
No. 441, No. 2-34090, No. 2-110558.
No. 2-130976, No. 2-139183, No. 2-229300, and British Patent No. 255546.
No. 861984, and H.H. E. Spencer
Et al., Journal of Photographi
c Science, Vol. 31, pp. 158-169 (1983).

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or in Japanese Patent Application Nos. 2-264447 and 2-26.
No. 4448 is added at the time of chemical sensitization.
It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like.
It is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more and 1 × 10
^-4 mol or less. The temperature of chemical ripening when the selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, pAg and pH of 50 ° C. or higher and 80 ° C. or lower are arbitrary. For example, the effect of the present invention can be obtained in a wide pH range of 4 to 9.

The silver halide emulsion of the present invention is sensitized with gold-selenium, and it is possible to achieve higher sensitivity and lower fog by sensitizing gold-sulfur-selenium in combination with sulfur sensitization. ..

The sulfur sensitization in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

The gold sensitization in the present invention is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time.

For the sulfur sensitization, known sulfur sensitizers can be used. Examples thereof include thiosulfates, thioureas, allyl isothiocyanates, cystines, p-toluene thiosulfonates, and rhodanines. Other US Pat. Nos. 1,574,944 and 2,41
0,689, 2,278,947, 2,7
No. 28,668, No. 3,501,313, No. 3,
656,955 specifications, German Patent 1,422,8
No. 69, Japanese Patent Publication No. 56-24937, Japanese Patent Laid-Open No. 55-45.
The sulfur sensitizers described in JP-A No. 016, etc. can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount is pH,
Although it varies over a considerable range under various conditions such as temperature and size of silver halide grains, it is preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁴ mol or less per mol of silver halide.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Typical examples include chloroaurate, potassium chloroaurate,
Auric trichloride, potassium auriothiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate,
Pyridyl trichlorogold is mentioned. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol per mol of silver halide.

At the time of chemical ripening, there are no particular restrictions on the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with the selenium sensitizer. There is no need to provide it,
For example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical aging, or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, and acetone and added.

The chemical sensitization by gold-selenium sensitization or gold-sulfur-selenium sensitization of the present invention is more effective when performed in the presence of a silver halide solvent.

The silver halide solvent which can be used in the present invention is, for example, US Pat. No. 3,271,
No. 157, No. 3,531,289, No. 3,57
4,628, JP-A-54-1019, and JP-A-54-15.
(A) Organic thioethers described in 8917, JP-A Nos. 53-82408, 55-77737, and 5
(B) thiourea derivative described in JP-A No. 5-2982, and (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-53-144319. , (D) imidazoles, (e) sulfites described in JP-A No. 54-100717,
(F) Thiocyanate.

Particularly preferred silver halide solvents are:
Examples thereof include thiocyanate, tetramethylthiourea and thiocyanate. The silver halide emulsion of the present invention contains thiocyanate. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol per mol of silver halide.
It is less than or equal to mol.

As the thiocyanate, for example, ammonium salt, potassium salt and sodium salt are preferably used.

The thiocyanate may be used alone or in combination with a gold sensitizer at the time of chemical sensitization. The thiocyanate may be added dividedly or continuously.

In the present invention, thiocyanate is more preferably used not only during chemical sensitization but also during grain formation or during the desalting step. For the use of thiocyanates in grain formation, see US Pat.
No. 434226.

The silver halide light-sensitive material of the present invention is I
SO sensitivity is preferably 100 to 3200, and 4
It is more preferably from 00 to 3200.

The hydrogen cyanide gas scavenger in the present invention is a compound that converts the hydrogen cyanide gas generated when a light-sensitive material is irradiated with light into a photographically inactive substance. Therefore, the scavenger should not release any substance that adversely affects the silver halide light-sensitive material as a result of capturing the hydrogen cyanide gas. Suitable hydrogen cyanide gas scavengers can be selected from noble metal inorganic or organic compounds. Particularly preferred are palladium (II or IV) and platinum (II or IV) compounds. Gold (I or III) compounds are also preferred. Compounds of rhodium (III), iridium (III or IV) and osmium (II, III or IV) are also effective, but higher amounts are required to achieve comparable effects.

Specific examples of useful inorganic or organic noble metal compounds include, for example, Gmelin Handbook (Gmeli Handbook).
n Handbook), commercial products, synthetic products, and in situ synthetic products should be used in such a purity that they do not adversely affect the photographic light-sensitive material.

Typical useful palladium compounds are, for example, radium (II) chloride, palladium (II) bromide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) thiocyanate, tetrachloropalladium ( I
I) acid salt (sodium salt, potassium salt, ammonium salt), hexachloropalladium (IV) acid salt, tetrabromopalladium (II) acid salt, hexabromopalladium (I)
V) acid salt, bis (salicylat) palladium (II) acid salt,
Bis (dithiooxalato-S, S ') palladium (II)
Acid salt, trans-dichlorobis (thioether) palladium (II), tetraamminepalladium (II) salt, dichlorodiamminepalladium (II), dibromodiamminepalladium (II), oxalatodiamminepalladium (II), dinitrodiamminepalladium (II), Bis (ethylenediamine) palladium (II) salt, dichloroethylenediaminepalladium (II) salt, bis (2,2'-bipyridine) palladium (II) salt, bis (1,10-phenanthroline) palladium (II) salt, tetranitropalladium ( II) acid salt, bis (glycinato) palladium (I
I), tetrakis (thiocyanato) palladium (II) acid salt, dichlorobis (phosphine) palladium (II), di-μ-chloro-bis [chloro (phosphine) palladium (II)], di-μ-chloro-bis [chloro] (Arsine)
Palladium (II)], and dinitrobis (arsine)
Palladium (II) is mentioned.

Typical useful platinum compounds are, for example, platinum (II) chloride, platinum (IV) chloride, hexafluoroplatinate (IV) acid salt, tetra-chloroplatinum (II) acid salt, hexachloroplatinum (IV) acid. Salt, trichlorotrifluoroplatinum (I
V) acid salt, tetrabromoplatinum (II) acid salt, hexabromoplatinum (IV) acid salt, dibromodichloroplatinum (II) acid salt, hexahydroxoplatinum (IV) acid salt, bis (oxalato) platinum (II) acid salt, Dichlorobis (oxalato) platinum (IV)
Acid salt, bis (thiooxalato) platinum (II) acid salt, bis (acetylacetonato) platinum (II) acid, bis (1,1,1)
1,5,5,5-hexafluoro-2,4-pentanedionato, platinum (II), bis (1,1,1-trifluoro-2,4-pentanedionato) platinum (II), tetrakis ( Thiocyanato) platinum (II) acid salt, hexakis (thiocyanato) platinum (IV) acid salt, bis {(Z) -1,2-dicyanoethylene-1,2-dithiolato} platinum (II) acid salt,
Dichlorobis (diethylsulfide) platinum (II), tetrachlorobis (diethylsulfide) platinum (IV), bis (glycinato) platinum (II), dichloroglycinatoplatinum (II) acid salt, dichlorobis (triethylphosphine) platinum (II) , Chlorohydridobis (triethylphosphine) platinum (II), tetraammineplatinum (II) salt, tetrachloroplatinum (II) salt, dichlorodiammineplatinum (I
I), trichloroammine platinum (II) salt, hexaammine platinum (IV) salt, chloropentammine platinum (IV) salt,
Tetrachlorodiammine platinum (IV), dinitrodiammine platinum (II), dichlorotetrakis (methylamine) platinum (IV) salt, dichloro (ethylenediamine) platinum (I
I), bis (ethylenediamine) platinum (II) salt, tris (ethylenediamine) platinum (IV) salt, dichlorobis (ethylenediamine) platinum (IV) salt, dichlorodihydroxo (ethylenediamine) platinum (IV), tetrakis (pyridine) platinum ( II) salt, dichlorobis (pyridine) platinum (I
I), bis (2,2′-bipyridine) platinum (II) salt, tetranitroplatinate (II) salt, chlorotrinitroplatinum (I)
I) acid salt, dichlorodinitroplatinum (II) acid salt, dibromodinitroplatinum (II) acid salt, hexanitroplatinum (IV) acid salt, chloropentanitroplatinum (IV) acid salt, dichlorotetranitroplatinum (IV) acid salt , Trichlorotrinitroplatinate (IV), tetrachlorodinitroplatinate (IV), dibromodichlorodinitroplatinate (IV), trichloro (ethylene) platinum (II), di-μ-chloro-bis { Chloro (ethylene) platinum (II) trans-dichloro (ethylene) (pyridine) platinum (II), bis [bis (β
-Mercaptoethylamine) nickel (II) -S, S "
-Platinum (II) salt, and dichlorodicarbonyl platinum (I
I) can be mentioned.

Gold (I or III), Rhodium (III), Iridium (III or IV) and Osmium (II, III or
The compounds of IV) can be mentioned in the same manner, for example, potassium tetrachloroaurate (III) and rhodium (II).
I) chloride, potassium hexachloroiridate (IV), potassium tetrachloroiridate (III) and potassium hexachloroosmate (IV).

The inorganic or organic compound of the noble metal is not limited to the above-mentioned specific examples as long as the effects of the present invention can be obtained.

The halogen gas scavenger in the present invention is a compound that converts the halogen gas generated when the photosensitive material is irradiated with light into a photographically inactive substance. Therefore, the scavenger should not release a substance that adversely affects the silver halide light-sensitive material as a result of capturing the halogen gas.

It is generally known that gelatin acts as a halogen gas scavenger, and that its action is a function of pH and pAg of the system. However, in the present invention, the following compounds are preferably present as halogen gas scavengers at any position in the sealed container of the photographic product.
That is, for example, sulfide compounds, nitrites, semicarbazides, sulfites, hydroquinones, ethylenediamine, acetone semicarbazone, p-hydroxyphenylglycine. Particularly preferred compounds include compounds represented by the following general formula (H).

[0079]

[Chemical 11] In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a group capable of substituting for a benzene nucleus.

Examples of the substituent in the general formula (H) include a halogen atom (eg, fluorine, chlorine, bromine atom), an alkyl group (eg, methyl, ethyl, n-propyl, t-butyl, n-amyl, i). -Amyl, n-octyl, n-dodecyl, n-octadecyl group, particularly preferably having 1 to 32 carbon atoms), alkenyl group, aryl group,
Acyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarboxamide group, arylcarboxamide group, acylsulfonamide A group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group and an arylacyloxy group are preferable.

These groups may be further substituted with the same substituents as those mentioned above.

Specific examples of the compound represented by the above general formula (H) (the following "Chemical formula 12" to "Chemical formula 16") are shown below.

[0083]

[Chemical formula 12]

[0084]

[Chemical 13]

[0085]

[Chemical 14]

[0086]

[Chemical 15]

[0087]

[Chemical 16] The addition position of the hydroquinone which is a halogen gas scavenger may be any of a protective layer, an intermediate layer, a non-photosensitive layer such as a back layer provided on the side opposite to the emulsion surface of the film, or a silver halide emulsion layer. .. More preferably, it is added to a layer more distant from the support on the emulsion layer side of the support.

The amount of halogen gas scavenger added is 0.05 to 1 g / m ² , more preferably 0.1 to 1 g / m ² .
It is 0.5 g / m ² .

In the present invention, the hydrogen cyanide gas scavenger may be located at any position within the sealed container of the silver halide photographic product. It may be formed by coating or kneading on the inner surface of the sealed container, or may be formed by coating or kneading on the parts forming the light-shielding container. Particularly preferably, the hydrogen cyanide gas scavenger is present in the photographic light-sensitive material. The photographic light-sensitive material is usually a support, a back layer, an emulsion layer, a surface protective layer, an intermediate layer,
Although consisting of an antihalation layer, the hydrogen cyanide gas scavenger of the present invention may be applied by directly adding to these layers or may be applied alone with a suitable solvent or binder.

As a method of adding the hydrogen cyanide gas scavenger, a method usually used when adding an additive to a photographic light-sensitive material can be applied. For example, a water-soluble compound is prepared as an aqueous solution having an appropriate concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters and amides. Of these, it can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

Back layer, emulsion layer, surface protective layer, intermediate layer,
And the antihalation layer is usually a dispersion with a binder, but useful binders include naturally occurring polymeric vehicles such as gelatin and cellulose derivatives and synthetic vehicles such as polyvinyl alcohol and its derivatives, acrylate and methacrylate polymers. , Butadiene-styrene polymers and similar materials. When the hydrogen cyanide gas scavenger is directly added to these layers, it is necessary to carefully select the conditions such as the concentration and pH of the binder according to the type and amount of the hydrogen cyanide gas scavenger used. Generally, the metal compound interacts with gelatin, and the viscosity of the system may increase remarkably depending on the conditions. For example, regarding the interaction between the palladium (II) ion and gelatin, the Journal of the Photographic Society of Japan, 34, 159 (1971).
Keiichi Tanaka, Journal of the Photographic Society of Japan, Vol. 37, page 133 (197)
4) Keiichi Tanaka, Vol. 39, page 73 (19)
76) Keiichi Tanaka, Journal of Photographic Science, Vol. 21, page 134 (1973) Keiichi Tanaka, and Journal of Photographic Science, Vol. 26, page 222 (1978) Keiichi Tanaka. Since the palladium (II) ion has a strong bond with the amide bond and the amino acid residue of gelatin, it may generate a foreign substance in the form of gelatin in some cases, depending on the conditions. It is preferable to select and use.

The addition amount of the hydrogen cyanide gas scavenger in the present invention should be determined within a range where the effect of the present invention is remarkably exhibited, but it is preferably 1/10 per 1 mol of thiocyanate contained in the portion which can be irradiated with light. More than a mole. More preferably, the molar ratio of thiocyanate contained in the light-irradiable portion is 1/2 mol or more and 100 or more.
It is not more than 1 mol, and particularly preferably 1 mol to 10 mol.

In the silver halide photographic product of the present invention, the photographic light-sensitive material is stored in a hermetically sealed container, a part of the light-sensitive material is placed in a position where light can be irradiated after sealing, and the rest is placed in a light-shielding position. Air is circulated between the irradiated portion and the light-shielded portion.

In the present invention, the light-shielding container includes a cassette for sheet film, but is typically a patrone for roll film. A roll film patrone has a spool shaft around which a silver halide light-sensitive material is wound in a roll shape, and a film outlet through which the light-sensitive material is taken in and out, and the spool is rotated around an axis. It has a patrone body that can be stored freely. In order to shield light, the spool has a flange so that it can be removed from the gap between the spool shaft and the cap provided on the side edge of the typically cylindrical body of the patrone body. The external light that is about to enter the container is blocked. Further, it is preferable that a light-shielding member is provided at the exit of the film so that the film can be pulled out and rewound smoothly. This shading member is
1-34526.

As a silver halide photographic product of this type, for example, as shown in FIG. 1, a roll film of 135 format, which is currently the mainstream, corresponds. That is, the silver halide photographic light-sensitive material is housed in a metal cartridge 2 with a plastic spool 1 as a mandrel and partially pulled out from a film pull-out portion 3 via a light-shielding ribbon. Usually, a few cm of film is pulled out for the convenience of film loading, and this part corresponds to the position where light can be irradiated,
Air passes through the light-shielded portion through the gap between the film pull-out portion 3 or the parrotone 2. However, 4 in the figure
Indicates the extracted part.

The cartridge 2 containing the silver halide photographic light-sensitive material is sealed by a cartridge case 5 and a cartridge cap 6. The hermetically sealed container is designed to block harmful gases to the photosensitive material and suppress excessive permeation of water vapor, but the permeability of gas and water vapor is greatly affected by the structures and materials of the cartridge case 5 and the cartridge cap 6. It It is preferable that the humidity in the sealed container is kept constant, and in the present invention, the relative humidity at 25 ° C. is 55% or more, more preferably 55%.
The effect of the invention is remarkable when it is from 70 to 70%, particularly preferably from 55 to 65%.

It is meant that the humidity in the sealed container is kept constant.
12 at 25 ° C when the humidity difference between the outside air and the inside of the case is 20%
It means a state where the humidity change inside the case is 10% or less after a lapse of months.

It is preferable for the present invention to keep the humidity near a normal humidity in a sealed container. Specifically, at 25 ° C., the relative humidity in the sealed container is preferably 50% or more and 70% or less, more preferably 55% or more and 68% or less.

The equilibrium humidity referred to in the present invention is a value measured at 25 ° C. and can be measured by a conventional method (equilibrium humidity is
For example, it can be measured by a capacitance type humidity measuring instrument of a Humicap humidity sensor manufactured by VAISALA. ) In the present invention, the closed container is light transmissive. Light transparency means that the part drawn from the film drawing part
It means that it can be substantially exposed to external light, and its average transmittance is preferably 1% or more, more preferably 10%.
That is all.

The plastic material used in the present invention includes addition polymerization of an olefin having a carbon-carbon double bond, ring-opening polymerization of a small ring compound, polycondensation (condensation polymerization) of two or more polyfunctional compounds, and polycondensation. It can be produced using a method such as addition and condensation of a phenol derivative, a urea derivative or a melamine derivative with a compound having an aldehyde.

The raw material of the plastics material is, for example, styrene, as an olefin having a carbon-carbon double bond.
α-methylstyrene, butadiene, methyl methacrylate, butyl acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylcarbazole, N-vinylpyrrolidone, vinylidene cyanide, ethylene, and propylene are typical examples. Be done. In addition, as the small ring compound, for example, ethylene oxide, propylene oxide, glycidol, 3,3-bischloromethyloxetane, 1,4-dioxane, tetrahydrofuran, trioxane, ε-caprolactam,
Typical examples are β-propiolactone, ethyleneimine, and tetramethylsiloxane.

As the polyfunctional compound, for example, carboxylic acids such as terephthalic acid, adipic acid and glutanoic acid, isocyanates such as toluene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, alcohols such as ethylene glycol, propylene glycol and glycerin. Typical examples include amines such as hexamethylenediamine, tetramethylenediamine, paraphenylenediamine, and epoxies. Typical examples of the phenol derivative, urea derivative and melamine derivative include phenol, cresol, methoxyphenol, chlorophenol, urea and melamine. Further, typical examples of the compound having an aldehyde include formaldehyde, acetaldehyde, octanal, dodecanal, and benzaldehyde. These raw materials may be used alone or in combination of two or more, depending on the target performance.

When a plastic material is produced using these raw materials, a catalyst or a solvent may be used.

As the catalyst, (1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylpropane), benzoyl peroxide, cyclohexanone peroxide, Radical polymerization catalyst such as potassium persulfate, sulfuric acid, toluenesulfonic acid, tolufluorosulfuric acid, perchloric acid, trifluoroboron, cationic polymerization catalyst such as tin tetrachloride, n-butyllithium, sodium / naphthalene, 9-fluorenyllithium Anionic polymerization catalysts such as phenylmagnesium bromide, triethylaluminum / tetrachlorotitanium-based Ziegler-Natta catalysts, sodium hydroxide, potassium hydroxide, potassium metal and the like are used.

The solvent is not particularly limited as long as it does not inhibit the polymerization, and examples thereof include hexane, decalin, benzene, toluene, cyclohexane, chloroform, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran and the like.

For molding the plastics of the present invention, a plasticizer is mixed with the plastics as needed. Typical examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerocratone, di-n-octyl succinate, bromonaphthalene, and butyl palmitate. Is.

Specific examples of the plastic material used in the present invention are shown below, but the invention is not limited thereto.

P-1 Polystyrene P-2 Polyethylene P-3 Polypropylene P-4 Polymonochlorotrifluoroethylene P-5 Vinylidene chloride resin P-6 Vinyl chloride resin P-7 Vinyl chloride-vinyl acetate copolymer resin P-8 Acrylonitrile -Butadiene-styrene copolymer resin P-9 methyl methacrylic resin P-10 vinyl formal resin P-11 vinyl butyral resin P-12 polyethylene phthalate P-13 teflon P-14 nylon P-15 phenol resin P-16 melamine resin Particularly preferred plastic materials for the invention are polystyrene, polyethylene, polypropylene.

The grain size of the emulsion used in the present invention is, for example, the equivalent circle diameter of the projected area using an electron microscope, the equivalent sphere diameter of the particle volume calculated from the projected area and the grain thickness, or the equivalent sphere diameter of the volume determined by the Coulter counter method. Can be evaluated by

As a scale for expressing the size distribution, a variation coefficient of the projected area circle equivalent diameter of particles or the sphere equivalent diameter of volume may be used. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 22% or less, more preferably 18% or less, and further preferably 15% or less.

The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When it is desired to accelerate the development / desilvering (bleaching, fixing and bleach-fixing) steps, silver halide grains having a high silver chloride content are desirable. Further, in the case of suppressing development appropriately, it is preferable to contain silver iodide. The preferable silver iodide content varies depending on the intended light-sensitive material. For example, 0.1 to 15 mol% is preferable for the X-ray sensitive material, and 0.1 to 5 mol% is preferable for the graphic arts and the micro sensitive material. In the case of a photographic light-sensitive material represented by a color negative, it is preferably a silver halide containing 1 to 30 mol% of silver iodide, more preferably 5 to 20.
Mol%, particularly preferably 8 to 15 mol%. The inclusion of silver chloride in the silver iodobromide grains is preferred for alleviating lattice distortion.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. The typical one is, for example, Japanese Patent Publication No.
3162, JP-A-61-215540, JP-A-60
These are core-shell type or double structure type grains having a halogen composition in which the inside of the grains and the surface layer are different as disclosed in JP-A-222845, JP-A-60-143331 and JP-A-61-75337. Further, it is not a simple double structure, but a triple structure as disclosed in JP-A-60-222844 or a multilayer structure of more than that, or a different composition on the surface of the core shell double structure particles. The silver halide can be thinly applied.

In order to give a structure to the inside of the particles, not only the wrapping structure as described above but also a so-called junction structure can be prepared. Examples of these are, for example, JP-A-59-133540 and JP-A-58-108526.
No., European Patent No. 199,290A2, JP-B-58-2
No. 4,772, and JP-A No. 59-16254.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or have a structure, it is important to control the halogen composition distribution between grains. A method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.
Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. For example, there is a correlation in which larger size particles have a higher iodine content, while smaller particles have a lower iodine content. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.

A normal crystal not containing twin planes is one of the preferable forms as the silver halide grains used in the present invention. In the case of normal crystal, a cube consisting of (100) plane, (11
An octahedron composed of 1) planes is disclosed in JP-B-55-42737 and JP-A-60-222842 (110).
A dodecahedral grain composed of planes can be used. In addition, the Journal of Imaging Scene
30: 247, (h11) plane particles typified by (211) as reported in 1986,
(Hh1) plane particles typified by (331), (210)
The (hk0) plane particles typified by the plane and the (hk1) plane particles typified by the (321) plane may be selected and used according to the purpose although the preparation method requires some devise.

The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. It is preferred to use tabular grains having aspect ratios greater than 1 in the present invention.

When the tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by the sensitizing dye, and the above-cited US Pat. No. 4,434,226.
The issue is detailed. 80% of the total projected area of the grain
The above average aspect ratio is preferably 1 or more and less than 100. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. The shape of tabular grains can be selected from triangles, hexagons, circles and the like. A regular hexagon with six sides of approximately equal length, as described in US Pat. No. 4,797,354, is a preferred form.

Dislocation lines can be observed with a transmission electron microscope. Particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations can be selected according to the purpose, but particles containing dislocations are preferred.

The silver halide emulsion used in the present invention is
It is preferable to carry out reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
Either a method of growing or aging in a low pAg atmosphere of ˜7 or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds.

During the production process of the emulsion used in the present invention,
It is preferable to use an oxidizing agent for silver. The oxidizing agent for silver refers to a compound that acts on a metal acid to convert it into silver ions.

Preferred oxidizing agents in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonates, and organic oxidizing agents such as quinones.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage, or during photographic processing, or for stabilizing photographic performance. it can. That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (Especially 4-hydroxy substitution (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes can be added. For example, US Pat. Nos. 3,954,474 and 3,982,947.
And those described in JP-B-52-28660 can be used. One of the preferred compounds is JP-A-63
There are compounds described in No. 212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization and before coating It can be added depending on the purpose. Addition during emulsion preparation to exert the original antifoggant and stabilizing effect, control grain habit, reduce grain size, reduce solubility of grains, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styrin dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, pyrroline, oxazoline, thiazoline,
Pyrrole, oxazole, thiazole, selenazole,
Nuclei such as imidazole, tetrazole, pyridine; nuclei in which these rings are fused with alicyclic hydrocarbon rings; and nuclei in which these nuclei are fused with aromatic hydrocarbon rings, that is, indolenine, benzindolenine, indole , Nuclei such as benzoxadol, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole and quinoline can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one, thiohydantoin, 2-thiooxazolidin-2,4-dione, thiazolidine-2,4
-5- to 6-membered heterocyclic nuclei of dione, rhodanine, thiobarbituric acid can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
7,862, 4,026,707, British Patents 1,344,281, 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12,375, and Japanese Patent Laid-Open No. 52-375. -110,618 and 52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-8-969 and 4,225,666.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, the addition of these said compounds separately, as taught in US Pat. No. 4,225,666,
That is, it is possible to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization.
It may be at any time during silver halide grain formation, including the method disclosed in U.S. Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

Although the above-mentioned various additives are used in the light-sensitive material of the present technology, various additives other than the above can be used according to the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (1978, 1).
February), the same Item 18716 (November 1979) and the same Item 307105 (November 1989), and the corresponding portions are summarized in the table below.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 996 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to page 996, right column to supersensitizer, page 649, right column, page 998, right column 4. Whitening agent Page 24 Page 998 Right column 5. Antifoggants, pages 24 to 25, page 649, right column, page 998, right column to and stabilizer, page 1000, right column 6. Light absorber, pages 25 to 26, page 650, right column to page 1003, left column, filter dye, page 650, left column, page 1003, right column, ultraviolet absorber 7. Anti-staining agent Page 25 Right column 650 Left to right column 8. Dye image stabilizer page 25 9. Hardener page 26 page 651 left column 1004 page right column to 1005 page left column 10. Binder page 26 same as above page 1003 page right column to page 1004 right column 11. Plasticizer and lubricant page 27 page 650 right column 1006 page left column ~ 1006 right column 12. Coating aid, pages 26-27 ibid. 1005 left column ~ surfactant 1006 left column 13. Static page 27 ibid. 1006 right column ~ inhibitor 1007 left column Halogenation of the invention The higher the photosensitivity of the silver halide photographic light-sensitive material, the greater the effect of silver photographic products on improving photographic performance. This is obvious considering the mechanism that hydrogen cyanide gas is generated from the light-sensitive material by light irradiation.

The silver halide photographic light-sensitive material of the present invention preferably has a specific photographic sensitivity of 100 or more, particularly preferably a specific photographic sensitivity of 320 or more.

Here, the specific photographic sensitivity means, for example, Japanese Patent Laid-Open No.
It is the sensitivity determined according to the test method according to ISO sensitivity described in 3-1000453. (JIS K
The effect of improving the photographic performance of the silver halide photographic product of the present invention (according to 7614-1981) is remarkable when the silver halide photographic light sensitive material is a color photographic light sensitive material.

Particularly in color negative photographic light-sensitive materials, the amount of silver halide grains is generally stoichiometrically excessive with respect to the amount of couplers in order to increase the number of starting points and improve the image quality. The present invention is extremely effective because an increase in fog causes a serious problem since it causes a decrease in S / N ratio.

In the case of a silver halide color photographic light-sensitive material, at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer is provided on a support. The number of layers of the silver halide emulsion layer and the non-photosensitive layer and the order of the layers are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the sensitivities are gradually decreased toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541, No. 62-206543
As described in the above publication, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As specific examples, for example, from the farthest side from the support, a low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive Layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / R
H / RL order or BH / BL / GH / GL / RL /
It can be installed in the order of RH.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a middle layer in the lower layer. A silver halide emulsion layer having a photosensitivity lower than that of the silver halide emulsion layer may be arranged, and the photosensitivity may be gradually decreased toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer, medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

Also, in the case of four layers or more, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having different characteristics of at least one of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add to the light-sensitive material the compounds described in No. 7 and No. 4,435,503, which can be immobilized by reacting with formaldehyde.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Application Laid-Open No. 1-1060.
No. 52, it is preferable to include a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 is contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
The ones described in EP 249,473A are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,351.
897, European Patent 73,636, US Patent 3,
061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238 and JP-A-6-62238.
0-35730, 55-118034, 60-
185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4 , 296,200,
No. 2,369,929, No. 2,801,171
No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
No. 08, No. 4,334, 011, No. 4,327,
173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A,
U.S. Pat. Nos. 3,446,622 and 4,333,9
No. 99, No. 4,775, 616, No. 4,451,
No. 559, No. 4,427,767, No. 4,69
No. 0,889, No. 4,254,212, No. 4,2
Those described in 96,199 and JP-A No. 61-42658 are preferred.

Typical types of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409. No. 320, No. 4,576,910,
British Patent 2,102,137, European Patent 341,1
88A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Section VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in No. 6,368 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, Item VII-F and No. 307105, VII
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As couplers which imagewise release a nucleating agent or a development accelerator upon development, British Patent No. 2,093
7,140, 2,131,188, JP-A-59.
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds which release, for example, a fogging agent, a development accelerator and a silver halide solvent by a redox reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers described in U.S. Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
No. 185950, JP-A No. 62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 313, 313. No. 308A, a coupler that releases a dye that recovers color upon removal, R.I.
D. No. 11449, 24241, JP-A-61-2
Bleaching accelerator releasing couplers described in US Pat. No. 1,012,247, ligand releasing couplers described in US Pat. No. 4,555,477, couplers releasing leuco dyes described in JP-A-63-75747, US Pat. , 774,181, which release a fluorescent dye.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 1
Specific examples of the high boiling point organic solvent having a temperature of 75 ° C. or higher include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)). Phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), ester acid of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate), benzoic acid esters (eg 2-ethylhexyl benzoate, dodecyl benzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, 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, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541
274 and 2,541,230.

In the color light-sensitive material according to the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-6-257747 are used.
2-272248, and 1,2-benzisothiazolin-3-one, n- described in JP-A-1-80941.
Butyl p-hydroxybenzoate, phenol, 4
It is preferable to add various preservatives or antifungal agents such as -chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples are 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 which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured under the condition of humidity controlled at 25 ° C. and 55% humidity (2 days), and the film swelling speed T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een, et al., Photographic Science and Engineering (Photogr, Sci, E
ng. ), Vol. 19, No. 2, pp. 124-129, which can be measured by using a swellometer (swelling meter) of the type. T _1/2 was treated with a color developer at 30 ° C. for 3 minutes and 15 seconds. 90% of the maximum swollen film thickness that reaches at times is defined as the saturated film thickness, and is defined as the time until the saturated film thickness reaches 1/2.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer includes, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener,
It is preferable to contain a binder, a plasticizer, a lubricant, a coating aid, and a surface active agent. The swelling ratio of this back layer is 1
50 to 500% is preferable.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
No. 18716, page 51, left column to right column, and the same No. 307
Development processing can be carried out by a usual method described on page 880-881.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an aqueous alkaline water solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and representative examples thereof include 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-methoxyethylaniline and their sulfates, hydrochlorides or p-toluene Examples include sulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazone, phenylsemicarbazides, 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, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-
Hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. This black-and-white developer contains a known black-and-white developing agent, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-p-.
Aminophenols such as aminophenol can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and 500 ml can be obtained by reducing the bromide ion concentration in the replenishing solution.
It can also be: To reduce the amount of replenishment,
It is preferable to prevent liquid evaporation and air oxidation by reducing the contact area of the treatment tank with air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between processing liquid and air (cm ² )] ÷
[Volume of Treatment Liquid (cm ³ )] The aperture ratio is preferably 0.1 or less, and 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 surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time 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. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Aminopolycarboxylic acids or complex salts of citric acid, tartaric acid and malic acid can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetate iron (III) complex salts are used from the viewpoint of rapid treatment and prevention of environmental pollution. preferable. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, which have a mercapto group or a disulfide group.
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927 54-35, 727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ion and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferable because of their large accelerating effect, and particularly, US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP-A-53
The compounds described in -95,630 are preferred. Further, the compounds described in US 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 light-sensitive material for photographing.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to increase the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. 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, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect or eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used, such as coupler), application,
Further, it can be set in a wide range depending on the washing water temperature, the number of washing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in Journal of the So
ciency of Motion Picture a
nd Television Engineers, Vol. 64, P.n. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above document, the amount of washing water can be significantly reduced,
The increase in the residence time of water in the tank causes problems such as bacteria breeding and the produced floating substances adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-28
The method of reducing calcium ion and magnesium ion described in No. 8,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described in Hiroshi Horiguchi, "Fungicide and Antifungal Agent". Chemistry "(19
1986) Sankyo Publishing, Sanitary Technology Society, "Sterilization, sterilization, and antifungal technology of microorganisms" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Encyclopedia of antibacterial and antifungal agents" (1986) The disinfectants described can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and as an example, it is used as a final bath of a color light-sensitive material for photographing. Mention may be made of a stabilizing bath containing a dye stabilizer and a surfactant. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material according to the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13-324, the aldol compounds described in JP-A No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628. ..

The silver halide color light-sensitive material according to the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
Typical compounds are JP-A Nos. 56-64339 and 57-57.
144447 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention comprises
For example, U.S. Pat. No. 4,500,626, JP-A-60
-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056 and European Patent 210,660A2.

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

[0202]

【Example】

Example 1 (Preparation of Emulsion) Emulsion I: 1.0 liter of 0.7% aqueous solution of inactive bone gelatin containing 0.05 mol of potassium bromide (the same applies per liter of solution) was kept at 60 ° C. and stirred. However, a 1.95 molar aqueous solution of potassium bromide and a 1.9 molar aqueous solution of silver nitrate were added thereto by the double jet method at the same constant flow rate for 80 seconds (consuming 4.4% of total silver nitrate). 400 ml of 9% deionized gelatin solution
After that, the temperature was raised to 75 ° C. After adding 1.52 mol of silver nitrate aqueous solution to adjust pBr to 2.25 (consuming 3.1% of total silver nitrate), 14.7N ammonia aqueous solution was added to adjust pH to 8.3, and after physical ripening, The pH was adjusted to 5.2 again by adding 1N nitric acid. Potassium bromide 1.34
Mol and an aqueous solution containing 0.16 mol of potassium iodide and a 1.9 mol silver nitrate aqueous solution at the same time while accelerating the flow rate (the flow rate at the end was 3.5 times that at the start), and the pBr was 1.56. Was added while keeping (6 of total silver nitrate
2.4% consumed). 250 ml of 0.11 molar aqueous potassium iodide solution was added over 5 minutes, and after the addition was completed, 1
After 0 minutes, a 1.34 molar aqueous solution of potassium bromide and silver nitrate 1.
A 9 molar aqueous solution was simultaneously applied at a constant flow rate for 15 minutes,
Br was added while keeping it at 2.42 (30.
1% consumed). Then, it is desalted by an ordinary flocculation method to obtain tabular silver iodobromide grains having an average grain diameter / thickness ratio of 6.0 and a sphere equivalent diameter of 0.85 μm (average silver iodide content: 8.9 mol% ) Was prepared. When the particles were observed with a transmission electron microscope, it was confirmed that dislocation lines were mainly contained in the fringe portions of the particles.

Emulsion I was added to spectral sensitizing dyes ExS-4, ExS-5 and ExS- used in the ninth layer of the photosensitive layer composition described below.
Emulsion 1 and 2 were prepared by the addition of No. 6 and optimal chemical sensitization by either of the following two methods. Here, “optimum” means that the sensitivity is highest when exposed for 1/100 second. Emulsion 1. (Gold-sulfur sensitization): 2.2 × 10 ⁻³ mol of sodium thiocyanate, 1.5 × 10 ⁻⁶ mol of chloroauric acid and 1.4 × sodium thiosulfate per mol of silver halide.
Optimum chemical sensitization was carried out at 56 ° C by adding 10 ^-5 mol. Emulsion 2. (Gold-sulfur-selenium sensitization): 2.2 × 10 ⁻³ mol of sodium thiocyanate / 2.2 × 10 ⁻⁶ mol of chloroauric acid and 1.0% of sodium thiosulfate per mol of silver halide.
× ^-5 mol and selenium sensitizer (Compound 40) 1.5 × ^-6
Optimum chemical sensitization was carried out at 56 ° C. by adding mol. (Preparation of Photosensitive Material Sample) Onto an undercoated cellulose triacetate film support, each layer having the composition as shown below was multilayer coated to prepare Sample 101 which is a multilayer color photosensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) 1st layer (antihalation layer) Black colloidal silver 0.18 gelatin 1.40 ExM-1 0.18 ExF-1 2.0x10 ^-3 HBS-1 0.20 2nd layer (intermediate) Layer) Emulsion G Silver 0.065 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04 Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ⁻⁵ ExS-3 3.1 × 10 ^{− 4} ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87 4th layer (medium speed red-sensitive emulsion layer ) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.060 ExC -3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high Sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁴ ExS-3 3.4 × 10 ⁻⁴ ExC-1 0.12 ExC− 3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20 6th layer (intermediate layer) Cpd-1 0. 10 HBS-1 0.50 gelatin 1.10 7th layer ( Speed green-sensitive emulsion layer) Emulsion C silver ^{0.35 ExS-4 3.0 × 10 -5} ExS-5 2.1 × 10 -4 ExS-6 8.0 × 10 -4 ExM-1 0.010 ExM- 2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium speed green emulsion layer) Emulsion D Silver 0.80 ExS -4 3.2x10 ^-5 ExS-5 2.2x10 ^-4 ExS-6 8.4x10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ⁻³ Gelatin 0.90 9th layer (high sensitivity green emulsion layer) Emulsion 1 (gold-sulfur sensitized) Silver 1.25 ExS-4 3.7 × 10 ^{− 5 ExS-5 8.1 × 10 -5} ExS-6 3.2 × 10 -4 ExC-1 0.010 ExM-1 0.0 0 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44 10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60 11th layer (low-sensitivity blue sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY -0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10 12th layer (medium speed blue emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78 13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4. ^{× 10 -4 ExY-2 0.10 ExY} -3 0.10 HBS-1 0.070 Gelatin 0.86 14th layer (first protective layer) UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00 Fifteenth layer (second protective layer) Emulsion G Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B- 2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 1.20 Gelatin 1.20 Furthermore, the storability, processability, pressure resistance, and mildew proofing are appropriately applied to each layer.
W-1 to improve antibacterial properties, antistatic properties and coating properties
To W-3, B-4 to B-6, F-1 to F-
17 and iron salt and lead salt are contained.

[0204]

[Table 1] In Table 1, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. It has been subjected. Specifically, each emulsion is shown in Table 2 below.
It is sensitized with gold and chalcogen under the conditions shown in. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0205]

[Table 2]

[0206]

[Chemical 17]

[0207]

[Chemical 18]

[0208]

[Chemical 19]

[0209]

[Chemical 20]

[0210]

[Chemical 21]

[0211]

[Chemical formula 22]

[0212]

[Chemical formula 23]

[0213]

[Chemical formula 24]

[0214]

[Chemical 25]

[0215]

[Chemical formula 26]

[0216]

[Chemical 27]

[0217]

[Chemical 28]

[0218]

[Chemical 29]

[0219]

[Chemical 30]

[0220]

[Chemical 31] A sample 102 was prepared in exactly the same manner as the sample 101 except that the emulsion 1 in the ninth layer of the sample 101 was replaced with the emulsion 2.

Summing up the thiocyanates used to prepare Emulsions A to G and 1,2, Samples 101 and 102 each contained 3 × 10 ^-3 mol of thiocyanate per mol of silver.

In Samples 101 and 102, sodium palladium (II) chloride was added to the sixth intermediate layer as the hydrogen cyanide gas scavenger of the present invention in an amount of 1 × 10 ^-5 mol based on the total amount of silver. Samples 103 and 104 were prepared in exactly the same manner.

In Samples 101 and 102, 1 × 10 ^-4 mol was added to the sixth intermediate layer as the hydrogen cyanide gas scavenger of the present invention with respect to the total amount of sodium palladium (II) chloride sodium chloride. Samples 105 and 106 were prepared in exactly the same manner.

Samples 101 to 106 were photographed in 135 formats and 24 sheets were processed into a cartridge format. After conditioning the humidity at 25 ° C and 60% relative humidity, store it in a transparent cartridge and a completely shaded cartridge in a dark place, attach a cap, and film units 1 to 12 shown in "Table 3" below.
It was created.

[0225]

[Table 3] The ratio of the area of the light-shielded portion housed in the cartridge and the area of the film drawing portion is 1: 0.05.

After irradiating them with light at 10,000 lux for 24 hours, they were irradiated with light at 25 ° C. for 60 hours.
% And 60 ° C. 60% for 3 days, cut out the part of the film that is stored in the patrone and shielded from light, and pass it through a continuous wedge at a color temperature of 4800 ° K to 1 /
It was exposed for 100 seconds and processed as described below. (Processing method) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 3 minutes 00 seconds 38 ° C water washing 30 seconds 24 ° C fixing 3 minutes 00 seconds 38 ° C water washing (1) 30 seconds 24 ° C water washing (2) 30 seconds 24 ° C. Stable 30 seconds 38 ° C. Drying 4 bottles 20 seconds 55 ° C. Next, the composition of the treatment liquid will be described. (Color developer) (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-methylalinine sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleaching solution) ( Unit g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia Water (27%) 6.5 ml Water was added to 1.0 liter pH 6.0 (fixer ) (Unit g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml Water was added to 1.0 liter pH 6.7 (Stabilizing liquid) (Unit g ) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-Triazole 1.3 1, 4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 The treated sample was subjected to concentration measurement with a green filter, and 60 ° C 6
The increase in fog and the change in sensitivity of the film stored at 0% for 3 days were determined and shown in Table 4. At this time, the change in sensitivity is represented by the relative value of the logarithm of the exposure amount required for increasing the optical density by 0.15 from the fog density, and the light exposure was performed at 25 ° C. 60 ° C.
The sensitivity of the film unit 1 stored for 3 days under the condition of 100% was shown as 100.

[0227]

[Table 4] The following are clear from Table 4. When light is irradiated in a transparent cartridge case and stored at 60 ° C. and 60%, abnormal fog occurs, and the degree thereof is remarkable when a selenium-sensitized silver halide emulsion is used. In the film unit in which a palladium salt was added to the intermediate layer of the sixth layer in an amount of 1/15 molar equivalent of thiocyanate contained in the part which can be irradiated with light, an increase in fog and a decrease in sensitivity due to irradiation with light in a transparent cartridge case were observed. Not much improved, but 2
With the film unit added at / 3 molar equivalent, a remarkable improvement is obtained. The effect of the palladium salt on the generation of fog and the decrease in sensitivity upon irradiation with light in the transparent cartridge case is remarkable in the film unit using the selenium-sensitized silver halide emulsion. Example 2 With respect to the sample 106, Cpd− was formed in the 11th, 12th, and 13th layers.
3 to 0.07, 0.015, 0.02 g / m ² respectively
Sample 107 was prepared in exactly the same manner except that it was added.

The sample 107 was processed and subjected to humidity control in the same manner as in Example 1 to prepare a film unit 13, and the same experiment and treatment were carried out. The obtained results are shown in "Table 5" below.

[0229]

[Table 5] From the results in Table 5, it can be seen that the hydroquinone derivative known as a halogen gas scavenger further contributes to the reduction of abnormal fog. Example 3 By changing the humidity control conditions of Samples 102 and 106,
The film units 14 to 21 were processed in the same manner as above, and the same experiment and treatment were performed. The obtained results are shown in "Table 6" below.

[0230]

[Table 6] From the results of Table 6, it can be seen that abnormal fog is less likely to occur when the humidity in the cartridge case is low, and therefore the effect of the present invention is remarkable when the relative humidity is 55% or more. Example 4 When the experiment of Example 1 was replaced by the following black and white development process, it was confirmed that no remarkable abnormal fog occurred in the black and white development process. Therefore, the effect of the present invention is particularly remarkable when color development processing is performed. (Developer) Metol 2 g Sodium sulfite 100 g Hydroquinone 5 g Borax-10H ₂ O 2 g Water was added to 1 liter (Processing method) After developing with the above-mentioned developer at 20 ° C. for 7 minutes, stopping, fixing, washing with water by a usual method, dry.

[0231]

As described above in detail, according to the present invention, the sensitivity and the graininess are excellent, and the fluctuations in the sensitivity and the fog are small during the storage aging period after the production of the light-sensitive material until it is used. It is possible to provide a silver halide photographic product stored in a transparent case.

[Brief description of drawings]

FIG. 1 13 as a silver halide photographic product according to the present invention
This is an explanatory view of a 5-format roll film, and this drawing is shown with the cartridge case 5 and the cartridge cap 6 opened for convenience of description.

[Explanation of symbols]

1 ... Spool, 2 ... Patrone, 3 ... Film drawer,
4 ... pulled out portion, 5 ... Patrone case, 6 ... Patrone cap.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0227

[Correction method] Change

[Correction content]

[0227] The following are clear from Table 4. When light is irradiated in a transparent cartridge case and stored at 60 ° C. and 60%, abnormal fog occurs, and the degree thereof is remarkable when a selenium-sensitized silver halide emulsion is used. In the film unit in which a palladium salt was added to the intermediate layer of the sixth layer in an amount of 1/15 molar equivalent of thiocyanate contained in the part which can be irradiated with light, an increase in fog and a decrease in sensitivity due to irradiation with light in a transparent cartridge case were observed. Not much improved, but 2
With the film unit added at / 3 molar equivalent, a remarkable improvement is obtained. The effect of the palladium salt on the generation of fog and the decrease in sensitivity upon irradiation with light in the transparent cartridge case is remarkable in the film unit using the selenium-sensitized silver halide emulsion. Example 2 With respect to the sample 106, Cpd− was formed in the 11th, 12th, and 13th layers.
3 to 0.07, 0.015, 0.02 g / m ² respectively
Sample 107 was prepared in exactly the same manner except that it was added.

Claims (2)

[Claims] 1. A support is provided with at least one silver halide emulsion layer containing a silver halide emulsion chemically sensitized in the presence of a gold sensitizer and a selenium sensitizer and a thiocyanate. A silver halide light-sensitive material, a light-shielding container containing the light-sensitive material, and a light-transmissive sealed container containing the light-shielding container, the light-sensitive material having a part thereof located outside the light-shielding container. In the silver halide photographic product having such a structure that gas can flow between the inside and the outside of the light-shielding container, a hydrogen cyanide gas scavenger is provided at any position in the sealed container. Silver halide photographic product. 2. The silver halide photographic product according to claim 1, further comprising a halogen gas scavenger at any position in the sealed container.