JPS60263150A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent staining of a developing soln. and to reduce the tendency of a photosensitive material to change its performance even during its storage by incorporating a specific compd. in a photographic sensitive material. CONSTITUTION:This silver halide color photographic sensitive material contains a DIR compd. for producing a development inhibitor by the reaction with the oxidation product of a developing agent, and after flowing into the developing soln., said material stops its development inhibition action, and this compd. is represented by the formula shown here in which A is a group for releasing L1 and groups combining with it by the reaction of the oxidation product of the developing agent, and A represents a coupler or a hydroquinone component; Z is a fundamental component exhibiting the development inhibition action, and it is combined with A through the linking group L1; Y is substituent for exhibiting the development inhibition action; and a linking group L2 has a chemical bond cleft in the developing soln., is cleft with a nucleophilic reagent, such as hydroxyl ions or hydroxylamine, incorporated in the color developing agent as its component.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silver halide photographic material with excellent preservability.

(Background Art) In silver halide color photographic materials, a method is usually carried out in which an aromatic primary amine color developing agent oxidized by color development reacts with a coupler to form a dye.
This color reproduction method uses the subtractive color method (“The T
theory of thePhotographic
Processes ″4tthed.

ppJJj-362, edited by T.H. James). In this method, it is widely practiced to incorporate into the photographic light-sensitive material a compound that releases a development inhibitor in accordance with the density of the image during development. This compound generally reacts with the oxidation product of a color developing agent to release a development inhibitor, and typically contains a group in the active position of the coupler that has a development inhibitory effect when released from the active position. It is known as a so-called DIR coupler that introduces.

US Patent No. 31.2 Core is a DIR Kazoler.

ssa issue, 3.70/, 713, 3I6/j,
Compounds described in No. 306, J, T/7.2, No. 1, etc., as well as further improvements of these compounds, were published in Japanese Patent Publication No. 3
, t-34 (compounds described in No. 233) are known.As is well known from the above-mentioned specifications, DIR couplers improve the sharpness of color images by edge effects and improve color reproduction by multilayer effects. It is used for.

These DIR couplers have a drawback in that when the development inhibitor released during color development diffuses into the processing solution from the light-sensitive material, it accumulates in the processing solution, resulting in the processing solution exhibiting a development inhibiting effect. In the method of continuously processing a large amount of photosensitive material, that is, the processing method commonly used commercially,
It is difficult to obtain stable photographic performance, and contamination of the processing solution released from the DIR coupler trap has been a serious problem6.Therefore, in order to solve these problems, we have developed a method for releasing the coupler from the active site through a color development reaction. When desired, it becomes a compound with photoresistance suppressing properties, and after it flows out of the color developing solution, it decomposes into a compound that does not substantially affect photographic properties. Cazolar was proposed in JP-A-37-/J/Tap4<.

It is true that color photographic materials with excellent sharpness and color reproducibility were realized using this cazoler without contaminating the developer.

However, although photosensitive materials are stored for a long period of time after they are manufactured and before they are used, silver halide photographic materials containing the above-mentioned couplers suffer from increased fog, graininess, sharpness, and color reproduction during storage. There were cases where the properties deteriorated and there were problems in practical use.

(Object of the Invention) An object of the present invention is to provide a photosensitive material that does not cause developer contamination and whose performance does not change easily even during storage, and which is suitable for this purpose. It is an object of the present invention to provide a method for preserving, especially a method for packaging.

(Structure of the Invention) An object of the present invention is to generate a development-inhibiting group by the reaction of a developing agent with an oxidation product, and after this development-inhibiting group flows out into a developer, it substantially loses its development-inhibiting properties. This was achieved using a nine-silver halide photographic light-sensitive material containing a compound having the characteristics shown below (hereinafter referred to as the compound of the present invention) and stored at a relative humidity of 33% or less.

The effects of the present invention can be seen, for example, after storage at 300C for 1 month, or for about 7 days at 6o 0C, which is the case in a car exposed to direct sunlight.

In the present invention K, it is preferable to use U-seal packaging as a method of preserving the product at a relative humidity of 33% or less.

Sealed packaging as used in the present invention refers to moisture-proof packaging that is well known in the field of ordinary packaging. Packaging materials include metals and metal foils such as aluminum plates, tin plates, and aluminum foils, glass, polymers such as polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, polyamide, various polymers, and cellophane. Composite laminated materials (laminated materials in packaging terminology) made of materials such as paper and aluminum foil are used.

Sealing methods include adhesive methods using various adhesives,
A thermal fusion method such as heat sealing, or a method using a cartridge case, which is common in the photographic industry, can be used. Details of these sealing methods are described in 1 Food Packaging Technology Handbook'' Japan Packaging Technology Association Cm) p673-pAOta.

In the present invention, a cartridge case made of a polymer such as polyethylene or polypropylene is preferable for a roll-type photosensitive material, and a cartridge case made of polyethylene or the like is preferable for a sheet-type photosensitive material.

These sealed packagings may be performed in duplicate.

The storage humidity conditions of the present invention are more preferably below SO,
More preferably, the relative humidity is 4Aj% or less.

The relative temperature in the present invention is a value measured at 2j 0C, and the relative humidity can be measured by the conventional method K.

As a packaging method with a lower relative humidity as in the present invention, the silver halide photographic light-sensitive material may be packaged in a low-humidity chamber, or the material may be dried more than usual when drying. Alternatively, a desiccant such as silica gel may be placed in the sealed container to reduce humidity.

When implementing the present invention, static failures often occur due to low humidity. To prevent this static failure,
It is particularly preferable to add a fluorine compound, which is well known as an antistatic agent.

As a fluorine-based compound, for example,
/ J O, % Kaisho Ill; -7711, Tokukaisho! j
-6! Compounds described in tO12 and the like can be used.

Further, in order to prevent static failure, it is preferable that the outermost layer contains a matting agent. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the matting agent is 0.0! μ〜i
oμ is preferred. The amount to be added is /~300■/
m2 is preferred.

Further, it is preferable that the outer layer contains an ultraviolet absorber than the photosensitive halogenated burr layer. For example, benzotriazole compounds substituted with aryl groups (e.g. U.S. Patent J, 6
33.771), Hiro-thiacylidone compounds (for example, those described in U.S. Pat. No. 3,3'/4t, No. 7, U.S. Pat.
3! ), benzophenone compounds (for example, those described in JP-A No. 6-27rjt),
Cinnamate ester compounds (e.g. U.S. Patent J, 703)
．． No. 101, J, No. 707.371)
, butadiene compounds (e.g. US patent≠, ops, λλ
Alternatively, benzoxidol compounds (such as those described in U.S. Pat. Additionally, U.S. Patent 3.
≠Tata, No. 762, JP-A-54A-≠IjJj, JP-A-Sho II-///RI-412, JP-A-Sho SR
-/7133/ polymerized ultraviolet absorbers, etc. can be used.

The compounds used in the present invention are disclosed in Japanese Patent Application Laid-Open No. 7-1-127-1
It is described that 4t≠, and can preferably be represented by the following general formula (1), and is a type of so-called IR compound.

General formula ([) % formula %) In the above formula, it represents a compound, coupler component or hydroquinone component, which releases less than 1 shim by reaction with the oxidation product of the drug, and is a favorable coupler component. Z represents a basic moiety of a compound exhibiting a development inhibiting effect, and is bonded to the coupling position of the coupler directly (when a=J) or via the linking group Ll (when a=/).

Y represents a substituent that is bonded to Z via the linking group L2 and exhibits the development inhibiting effect of Z. The n linking group represented by L2 contains a 7'L chemical bond that is cleaved in the developer.

a represents 0 or l, and b represents 1 or ko. b
When represents λ, -L2-'Y may be the same or different.

The amount of the compound of the present invention added is o, oi-so mole, preferably 0,/~j mole, per mole of silver halide.

The yellow image-forming cazolyl residue represented by A includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type,
Malone ester monoamide type, benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, US Patent 3, r.
, No. 110, or coupler residues derived from Peter term-substituted acetamides or heterocycle-substituted acetates, or U.S. Pat. No. 3,770°1, British Pat.
No. 777, West German Patent (OLS) 2. go3. Coupler residues derived from acylacetamides described in Japanese Patent No. 60-/3, No. 73 or Research Disclosure No. 3737, or U.S. Patent No. a, O≠l, j7'1 Examples include the heterocyclic coupler residues described in .

The magenta image-forming coupler residues represented by humans include j-okigou 2-pyrazoline nucleus, pyrazolo-(/, j
-a] Coupler residues having a benzimidazole nucleus, a pyrazoloimidazole nucleus, a pyrazolotriazole nucleus, a pyrazolotetrazole nucleus, or a cyanoacetophenone type coupler residue are preferred.

The cyan color forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus.

Furthermore, the effect as a DIR coupler is the same even if the cazoler does not substantially form a dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. This type of coupler residue represented by A is US Patent ≠, 03
2. λ/3, Dohiro.

orr, 4M/No., J, 432.3'lj, No. 3, r, tr, No. 223 or No. 3. Examples include the coupler residues described in RI &/ and RIJRI issues.

The basic moiety of the development inhibitor represented by 2 includes a divalent heterocyclic group or a hetero-thio group, such as the following examples. A-(L,)a- group and -(L2
-Y) The substitution position of the b group is shown below.

2-Y 2-Y (L2-Y)b (L2-Y)b However, in the above formula, the substituent represented by X (included in the part O in general formula (1)) is a hydrogen atom , represents a halogen atom, an alkyl group, an alkenyl group, an alkenamide group, an alkenamide group, an alkoxy group, a sulfonamide group or an aryl group.

As an example of the group represented by Y in general formula CI), d1
Examples include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a heterozygous group.

Examples of the linking group represented by Ll in the general formula (1) include those shown below. A and Z −(
L2-Y), as shown below.

A-OCI(-Z-(L-Y)i 2 (U.S. Patent ≠, connection 4 described in Iko 6, 3-6) A-8CH2-Z-(L2-Y)b 1 A-QC- Z-(L-Y)b (Linking group described in West German Published Patent Application No. λ, 6λt, No. 315) (CH) -N-C-Z(-L2-Y)bJ 2c (West German Published Patent Application No. 2. ss , a linking group described in No. 7, C represents an integer of θ to λ.) In these DIR couplers (general formula CI), a==
/ case), the leaving group released after reacting with the oxidized form of the developing agent decomposes immediately or at a later time to form the development inhibitor (H-Z-(L2-Y) b) t-release f . t, 7
The effect of the present invention is the same as that of the DIR cazolar (when a=0 in the general formula ()) having no fund represented by 'j75 (L□).

In the general formula [1], the linking group represented by ■ and 2 is,
Contains chemical bonds that are cleaved in the developer solution.

Such chemical bonds include the examples listed in the table below. Since these are cleaved by nuclear reagents such as hydroxy ions or hydroxylamine, which are components in the color developing solution, the effects of the present invention can be obtained.

The chemical bonding modes Vi and Z shown in the preceding table are connected directly or via an alkylene group or (and) a phenylene group, and the other is directly connected to Y. When connecting to Z through an alkylene group or a phenylene group, the intervening divalent group may contain an ether bond, amide bond, carbonyl group, thioether bond, sulfone group, sulfonamide bond, or hyurea bond. good.

Among the couplers represented by the general formula (1), useful ones are those represented by the following general formula ([lJ, (t and (rv)). It has a strong effect and is preferable.

General formula Ctl) 2-Y General formula CIII) M 2-Y General formula (IV) 2-Y A, L2 and Y represented by general formula (II) are the same as those already explained in general formula [(] express meaning.

A1f'i represented by the general formula (In) represents a coupler residue other than the cyan coupler residue in A explained in the general formula (1).

A2V'i represented by general formula (IV), general formula (1)
It represents 7 uncoupler residues in A explained in .

X, L represented by general formulas (III) and (IV)
2 and Y represent the same meanings as explained in general formula (1).

(4) L6) (5) (7) (8) (1 (t)c5H,1 (9)(l l (12) (13) (14) (15) (16) NHCOC)ICONH (1)) N) (COCHCONH (18) (NHCOCHCONH (19) (24) (25) H3 (26) (27) COUCi-1□12CI-13 (28) O (29) H (30) (31) (32) ( 33) COOCH2CH2α (34) (35) CI(2COOCH2CH2SO2CH2CH3(36
) 0 (37) (38) H2 (39) (40) (41) (42) (43) (44) (46) In the present invention, when introducing the compound of the present application and a coupler that can be used in combination into the silver halide emulsion layer A known method, such as the method described in US Pat. No. 2,322,027, can be used. Also, Japanese Patent Publication No. 51-39853, Japanese Patent Application Publication No. 1973
The dispersion method using a polymer described in Japanese Patent No. 59943 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferred is sweat bromide wI containing from 2 mole % to 12 mole % silver iodide.

Average grain size of silver halide grains in a photographic emulsion (grain size is the grain diameter for spherical or approximately spherical grains, ridge length is the grain size for cubic grains, and expressed as the average calculated by the projected area) is not particularly limited, but it is preferably 3μ or less.

The grain size may be narrow or wide. Silver halide grains in photographic emulsions may have a regular crystal structure such as a cube or hexagon.5 They may also have a spherical or plate shape. It may have an irregular crystal form or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is P, Glafkides.
Written by Chimie et Physique Photo
ographique (published by Paul Monte1,
(1967), G. F. Duf in Pho
tographic Emulsion Chemises
try (The Focal Press, 196
6), V. L., Zeltkman et al.
AuthorMaking and Coating Photo
Graphic Emulsion (The Foc
Al PreJ SS, 1964). That is, acid method,
Any of the neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous quasi-method, a method of maintaining a constant ratio of I)Ag in the liquid phase in which the halogenated string is produced, ie, the so-called Chondrald double-jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, e.g.
Die Grundlagender Photogr
aphkschen Prozesse mit 5i
lber-halogeniden' (Akadem
ischeVerlagsgesellschaft,
1968), pp. 675-734, can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (eg, stannous salts);

Reduction sensitization method using amines, hydrazine derivatives, 5 formamidine sulfinic acid, silane compounds); Noble metal compounds (e.g. total complex salts, pt, [r, Pd, etc. in the periodic table)
A noble metal sensitization method using complex salts of metals of the above group can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as hendithiazolium salts, nitroimidazoles, nitrohenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotyphdiazoles, Aminotriazoles, hencytriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes, For example, triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (], 3.3a).

7) Tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)7 acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

Photographic processing of layers comprising photographic emulsions made using the present invention may be described, for example, in Research Disclosure No. 176 No. 2.
Any of the known methods and known treatment liquids as described on pages 8 to 30 can be used. The processing temperature is usually chosen between 18°C and 50°C, but 18°C
Lower temperatures or temperatures above 50°C may also be used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. As the color developing crude drug, known primary aromatic amine developers can be used.In addition, F, A, M
Photo-graphic Processes by ason
singChemistry (Focal Pres.
s publication, 1966), pages 226-229, US Patent 2.
No. 193.015, No. 2,592,364, JP-A-4
8-64.933 may be used.

Color developers may also contain pH agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobalt (■), chromium (VT), and 14 (n), peracids, quinones, and nitroso compounds.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

In the same or other photographic emulsion layers or non-light-sensitive layers of the photographic light-sensitive materials prepared using the present invention, other dye-forming couplers, i.e., aromatic primary amines, may be added in the color development process, in addition to the above compounds of the present application. A compound that can develop color by oxidative casopring with a developer (for example, a phenylenediamine derivative or an aminophenol derivative) may be used. For example, as a magenta coupler, 5-viladurone coupler, pyrazolobenzimidazole coupler, virazoloimidazole coupler, pyrazolo pyrazole coupler, pyrazolotriazole coupler, vilazolotetradurr coupler, cyanoacetyl coumaron coupler, open chain There are acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (e.g. hendiylacetanilides, bivaloylacetanilides F).
, etc., and examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized.

The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).
In addition to DIR couplers, there are also colorless DIRs in which the product of the force and pulling reaction is colorless and releases a development inhibitor.
It may also contain a coupling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added to two or more different layers. Of course it doesn't matter.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3, 5-
triacryloyl-hekihydro-3-triazine, 1
, 3-vinylsulfonyl-2-propatur, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone. Or they can be used in combination.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Example 1 In order to evaluate the effectiveness of the compound of the present invention, a multilayer color photosensitive material sample 1O/ was prepared on a cellulose triacetate support, each layer having the composition shown below.

The amount of emulsion coating was expressed as the amount of coating with scissors.

(Sample 101) 1st layer: Antihalation l- black colloidal silver 0. ．． 1197m2 Ultraviolet absorber U-/0. /, 2f! /m2 same [J
-20,/7 ta/m2 gelatin layer λ layer: intermediate layer λI! -d-t-pentadecylhydroquinone 0. /It/m2 coupler C
p-70,1197m2 Silver iodobromide emulsion 0. /! Gelatin layer containing f/m2 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion 0.72 f/m" Sensitizing dye I...7, OX/0 mole sensitizing dye per 7 moles of silver ■...Co for 1 mole of silver, 0 x io mole sensitizing dye■...Co for 1 mole of scissors, !×10 mole Sensitizing dye■...Co for 1 mole of silver, 0x10 molar coupler cp-/ 0.0.20t/m2 coupler
Cp -J O, OY J S' / m2 Casolar Cp-j 0031 97m2 Coupler Cp-4'
Gelatin layer containing 0,010 f/m2 Third layer: Red-sensitive emulsion layer Silver iodobromide emulsion /, A17m2 Sensitizing dye I... s, xXio moles per 1 mole of silver Sensitizing dye ■...・i, 5 xio mole sensitizing dye per 1 mole of silver ■...Co, /×10 per 1 mole of silver 4 mole sensitizing dye ■.../, j×10 mole coupler per 7 mole of silver Cp-10, Os/ri7 m2 Kazolar C
p-20, IO97m2 Coupler Cp-J O, OI! , 197m2 coupler Cp-II O,00! f/m2 oak 5- Cp-
Gelatin layer containing j 00014697m2 Third layer: Third red-sensitive emulsion layer Silver iodobromide emulsion /, Af/m2 Sensitizing dye s, 5xio moles per 7 moles of sensitizing dye silver Sensitizing dye ■...silver per 1 mole/, AXlo mole sensitizing dye ■...2.2X10 moles per mole of silver Sensitizing dye ■...per 7 mole of silver/, Axlo mole coupler cp-J O,030f/ m2 coupler (
:p-jOO 6th gelatin layer containing 12 fl/m2: Intermediate gelatin layer 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion o, ssy7m2 Sensitizing dye ■...3 per mole of silver , IrxlO molar sensitizing dye ■...3.0 x 70 molar per 7 mol of silver Sensitizing dye ■.../, 2 x 10' molar coupler per 1 mol of silver Cp-4o, λta f! /m2 coupler C
p-70,01i0f7m2 coupler 7 Cp-1o,
ojsf/m"Coupler cp-20,03g?/m"
R-th layer: Green-sensitive emulsion layer Silver iodobromide emulsion /, 197 m'' Sensitizing dye ■...2.7 x 10 mol per mol of silver Sensitizing dye ■... Per 1 mol of silver te2,/×10 molar sensitizing dye ■...1.5×10 molar coupler for 1 mole of silver Cp-40, 2397m2 coupler cp-70, 0/39/m” coupler Cp
-10,00F97m” coupler Cp-ta 0,01
Gelatin layer containing 0 f/m2 2nd layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion i, jy/m2 sensitizing dye Sensitizing dye 3.0 × no θ moles per 7 moles of silver sensitizing dye ■ ... λ, II x 10 mole per mole of silver Sensitizing dye ■... +jX10 mole coupler per mole of silver Cp-100,0709/m2 coupler c
p-70,0/3f! /m2 tricresyl phosphate o, po? Gelatin layer lth, containing /m2. N: No. -, b2. gelatin layer containing more yellow colloidal silver o, o4Ly7m2, j-t-pentadecylhydrokino7 0.11) J/ri/yn'' Layer ii: first blue-sensitive emulsion layer silver iodobromide emulsion Q, 3 pieces 2! m2 force i-ra-Cp-// 0.77 97m” coupler C
p-/2 0.0λry7m" Gelatin layer containing 2 0.12 27 m2 tricresyl phosphene 1st co-layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion 0.≠, y 7m2 Coupler cp-/ / 0.2! 17 m2 tricresyl phosphene) 0./7 f/m'? Sensitizing dye 73rd gelatin layer containing sensitizing dye 20.2 x 10 mol per 1 mol of sensitizing dye silver: Fine grain emulsion layer Iodinous odor Layer 14 gelatin layer containing silver oxide emulsion 0.2397 m2: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion /,001/m2 Coupler Cp-// o, 2 tuff m 2 tricresyl phosphate 0./II f! 7m 2 Sensitizing dye ■...3×1O mol per 1 mol of silver 1st layer: 1st protective layer UV absorber υ-/ 0./≠ 2!m2 Ultraviolet light Gelatin layer containing absorbent U-2o, λ-2!m2 76th layer: Protective layer Polymethyl methacrylate particles (diameter i, sμ) O, ost/m" Fluorine compound F-/ 0.0011f/m2 Silver iodobromide emulsion o,
In addition to the above composition, a gelatin hardening agent (1-l) and a surfactant were applied to each layer of the gelatin layer containing J o y 7m''.

Compound U-/U-coCp-/S O3N a cp-co ■ 001 (2CH2So2Cl(3 (t)C,)11, Cp-gCH2 Cp-j OCH2CH2SCHC,2H2, (n)ε Coo)I Open Cp -a polymer CI) -7 α Cp-r Cp-2 α, (t) Cp-7゜Cp-// Cp-/coH-//■, 780□N1((CH2)30CH□CH2N(CH
3) 3 sensitizing dye ■ (CH2)45o3Na ■ (CH2)3So3Na C2)15 ■ (Sample 102) The compound of the present invention ( 27L (6) and (2)
Sample 7 is the same as sample 10/ except that
0λ was created.

Width 3#CIK, length/20cINK in a dark place.
Holes for t-cut L and perforation were made, and several pieces of each were processed at the same time into the cartridge. This processed sample was
After being left for 21 hours at a relative humidity of 3%, they were placed in a cartridge case made of polypropylene and sealed under conditions of t''L≠O, 176, 50, and 55%, respectively. .The samples in these cartridge cases were heated to 30oC and ≠ while still in the cartridge case.
It was left at o 'C for ≠ months.

After that, the above sample was subjected to sensitometric exposure,
Color development processing as described below was performed and photographic properties #@ were examined. The results are shown in Table 1.

I took out a part of the cartridge case and measured the humidity inside the cartridge case with an ACE recorder at -56C.
%,! Flathead and! It was 7chi.

The same exposure process was also carried out for samples 10/ and 10λ which were not subjected to /ξ Trone preservation.

The development process used in the present invention was carried out as follows.

Color development process Time Temperature 1 Color development 3'/z” 3r0c2 Bleaching 1
．． '30 // 3 Washing 2' 4 Fixing 4A/5 Washing ≠' 6 Stable -/' Here, the compositions of each processing solution in the color development process are as follows.

Color developer water ♂θθml ≠-(N-ethyl-N-hydroxyethyl)amino-comethylaniline sulfate! ? Sodium sulfite jv Hydroxylamine sulfate 22 Potassium carbonate 309 J Potassium hydrogen carbonate l, -22 Potassium bromide /, 27 Sodium chloride, Mu 0.2? Trisodium nitrilotriacetate 1.22 Add water /
1 (pH 10, /) Bleach solution water to o Ml Ferric ammonium salt of ethylenediaminetetraacetic acid 100f Disodium ethylenediaminetetraacetic acid 10f Potassium bromide IjOf Acetic acid 10f Add water /l (p[(A,0) Fix Liquid water 100.1 Ammonium thiosulfate /!0? Sodium sulfite 10f Sodium hydrogen sulfite ko, j2 Add water 1l CpHA, o) Stable liquid water 700ml Formalin (37ch) j wl l Dryfel 3 xl Add water /l From Table 7, it is clear that according to the embodiment of the present invention, the fog does not become high during storage even in sample 102, which exhibits severe fogging during storage at relative humidity sr%. When the treated sample was observed under a microscope with a magnification of ≠θ, the relative humidity was #sr%,
Sample 10-1, which was stored under 000, not only had high fog, but also had significantly worse graininess compared to samples that were not stored in Cutrone. When stored at uo 0c, there was almost no deterioration in grain size or condition.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment July 2019 tz1-1 ``16'' Difference 1, Indication of Case From Showa 1997 Patent Application No. 1.20311 2, Name of Invention Silver Halide Photographic Light Sensitivity Material 3, Relationship with the case of the person making the amendment Patent applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Subject of amendment: Column 5 of “Detailed description of the invention” in the specification, “Invention of the invention” in the description of the contents of the amendment. The description in the "Detailed Explanation" section has been amended as follows.

1) Page 9, line 15 After "The amount of addition is" "When it is contained in the same layer as silver halide" Insert.

2) On page 9, line 17, after “is.” “When the compound of the present invention is not in the emulsion layer, the coating amount is 10
-7 to 10-3 mol/m2, preferably 10-
It is 6 to 1o-4 mol/m2. Insert J.

3) On page 62, line 17, "Do not store in cartridge" is corrected to J "4 left at 5°C for a month without storing in cartridge."

Procedural amendment letter Mr. Commissioner of the Patent Office 1゜Indication of the case Showa! Patent Application No. 1 JOftj No. 2,
Title of the invention Silver halide photographic light-sensitive material 3, Relationship to the amended person case Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. Contact information: 2-26-30 Nishi-Azabu, Minato-ku, Tokyo 106 Fuji Photo Film Co., Ltd. Tokyo Head Office Telephone: (406) 2537 4. Subject of amendment ``Detailed Description of the Invention'' in the specification Column 5: Contents of amendment The statement in the "Detailed Description of the Invention" column of the description is amended as follows.

(1) Insert the following statement in its entirety after page 6, line 7.

For example, heat a part of the heat-sealed package to melt it, immediately insert an electrical resistance hygrometer (Temperature and humidity recorder model AR-13YB manufactured by Ace Laboratories) into the package and seal it.
It is possible to measure the internal humidity while maintaining the temperature at 3°C. (2) The following statement is inserted after compound m (4#) on page 32.

cooc4)(e■　” After "Square" ", Participating bodies, etc." Insert.

Claims (1)

[Claims] Contains a compound that generates a development-inhibiting group by reaction with an oxidation product of a developer, and the development-inhibiting group substantially ceases to exhibit development-inhibiting properties after flowing out into a developer;
and a silver halide photographic material stored at a relative humidity of 66% or less.