WO2005024510A1 - Photographic film product - Google Patents

Abstract

A photographic film product that is excellent in storage stability in packaged form. In particular, a photographic film product comprising a silver halide color photographic lightsensitive material comprising a transparent support and, superimposed thereon, at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and nonsensitive layer, the silver halide color photographic lightsensitive material in rolled form housed in a cartridge and further in a packaging container, characterized in that in at least one of the sensitive layers, silver halide grains amounting to 70% or more of the total projected area comprise tabular silver halide emulsion having dislocation lines and that the silver halide color photographic lightsensitive material conditioned at a water content of 2.0 to 3.5% is housed in a packaging container in adequately sealed form in an atmosphere of 15 to 25ºC and 25 to 50% relative humidity.

Description

 Description Photographic PP

 The present invention relates to a photographic film product of a novel silver halide color photographic light-sensitive material, and more particularly, to a photographic film product having excellent storage stability in a packaging form. Background art

 In recent years, silver halide color photographic materials have been required to have high performance year by year, and have extremely high standards of high sensitivity and high image quality, such as high sharpness, high granularity, and excellent color reproducibility. In addition to the image quality characteristics, high storage stability is required to maintain stable quality even when stored in various environments for a long period of time.

In other words, recently, with the spread of compact zoom cameras and cameras with lenses, which are generally called single-use cameras, photographic equipment has become simpler and silver halide photographic materials can be used in various environments. As a result, it is anticipated that there will be more opportunities to be exposed in harsh environments, for example, in high-temperature conditions such as in summer cars, before use. In order to cope with such an environment, the silver halide color photographic light-sensitive material not only has excellent basic characteristics such as high image quality or high sensitivity as described above, but also has the above-mentioned conditions. Even when stored for a long time in a packaged condition, there is a growing demand for excellent storage stability that does not cause any change in performance. With the conventional technology, the Was not inadequate and further improvement was needed.

 In particular, in terms of high sensitivity, due to recent technological advances in digital cameras, in order to maintain the superiority of silver halide photographic light-sensitive materials, it is important to keep capri low and maintain storability. There is a need for higher sensitivity that is compatible with both.

 In order to provide higher stability, various techniques for improving the performance of silver halide grains, which are one of the main components of silver halide color photographic materials, have been studied in silver halide emulsions. A typical example is tabularization of silver halide grains.

 Tabular silver halide grains (hereinafter also simply referred to as tabular grains) have several photographic properties, in particular, a large ratio of surface area to grain volume (hereinafter referred to as specific surface area), (4) High sensitivity is expected in that the dye can be adsorbed on the surface.

 Technologies relating to tabular grains include, for example, U.S. Pat. Nos. 4,434,226, 4,439,520, 4,41,310, 4,433,048, and 4,433,048. No. 4,414,306, No. 4,459,353, Japanese Patent Publication No. Hei 4-36374, No. 5-16015, No. 6-44132, JP-A No. 6-43

No. 605, No. 6-43606, No. 6-214331, No. 6-222488, No. 6-230493, No. 6-258745, etc. disclose the manufacturing method and the technology used.

In order to more effectively bring out the advantages of the above tabular grains, it is effective to use tabular grains having a high aspect ratio. However, there has been a problem that it is difficult to combine with a dislocation line introduction technique, which is technically essential, in order to put a high aspect ratio tabular grain having an aspect ratio of 5 or more into practical use. Improvement of the photographic properties of silver halide emulsions by dislocation lines is well known in the art and has many technical disclosures (for example, see Patent Documents 1 to 6). Dislocation line technology has high expectations for higher sensitivity, and is now an essential technology for sensitizing tabular grains.

 However, a silver halide color photographic material using a tabular silver halide emulsion having a high aspect ratio with dislocation lines introduced therein has a maximum density when left in a high-temperature atmosphere in a sealed state for a long time. It has been found that this causes a decrease in gradation and softening of gradation. On the other hand, when the silver halide color photographic light-sensitive material is not stored in a sealed state but in an open high-temperature atmosphere, no significant performance deterioration is observed, so that the silver halide color photographic light-sensitive material has a high aspect ratio having dislocation lines. It can be said that this is a problem peculiar to a silver halide color photographic light-sensitive material using a tabular silver halide emulsion.

 Variations in the performance of silver halide photographic light-sensitive materials containing this high aspect ratio tabular grain tabular silver halide emulsion are caused by the fact that the specific surface area of the silver halide emulsion is large. It is presumed to be due to adsorption and desorption of various additives, but the detailed mechanism is not yet clear.

 Accordingly, an object of the present invention is to provide a photographic material having improved storage stability in a packaging form of a silver halide light-sensitive material using a tabular silver halide emulsion having a high aspect ratio and having introduced dislocation lines. To provide film products. (Patent Document 1)

 Unexamined Japanese Patent Publication No. Sho 633-220202

 (Patent Document 2)

Japanese Patent Application Laid-Open No. Hei 11-102 (Patent Document 3)

 Japanese Patent Application Laid-Open No. Hei 3-1 7 5 4 0

 (Patent Document 4)

 Unexamined Japanese Patent Publication No.

 (Patent Document 5)

 Japanese Patent Application Laid-Open No. Hei 6—2 7 564

 (Patent Document 6)

 Japanese Patent Application Laid-Open No. H11-19085885

Disclosure of the invention

 The above object of the present invention is achieved by each of the following constitutions.

 (1) A silver halide color photographic material having at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-light-sensitive layer on a transparent support is housed in a patrone in a roll. After that, in a photographic film product stored in a packaging container, at least one of the photosensitive layers contains a tabular silver halide emulsion having 70% or more of the total projected area of silver halide grains having dislocation lines. Containing the silver halide photographic light-sensitive material at a water content of 2.0% or more and 3.5% or less at a temperature of 15 ° C or more and 25% or less.

A photographic film product characterized by being stored in a sealed container in an atmosphere at a temperature of not more than 25 ° C and a relative humidity of not less than 25% and not more than 50%.

 (2) The tabular silver halide emulsion according to (1), wherein 50% or more of the total projected area contains tabular silver halide grains having an average aspect ratio of 8 or more. Photo film products.

(3) The tabular silver halide silver halide emulsion has a variation coefficient of a particle size distribution of a circle-converted diameter. The photographic film product according to (1), wherein the content is 15% or more and 30% or less.

 (4) The photographic film product according to (1), wherein the silver halide color photographic light-sensitive material contains a compound represented by the following general formula (1).

 Five

 General formula (1)

 Ten

 [In the formula, represents a hydrogen atom or an alkyl group. Q represents a group of nonmetal atoms necessary to form a 5- to 7-membered ring together with N and C = 0. A and B each represent a copolymerizable ethylenically unsaturated compound. x, y, and z each represent mol%, and 10 ^ x ^ 100, 0≤y≤90, and 0≤z90. The number average molecular weight is from 200 to 15200,000. ]

 (5) The photographic film product according to (1), wherein the packaging container is a sealed resin container made of a polyolefin-based resin.

(6) The photographic film product according to (1), wherein the packaging container is a moisture-proof bag having a moisture permeability of 20.0 g / m ^{2 to} 24 h (40 ° C. to 90 RH) or less.

 20

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto. The present inventors have conducted intensive studies in view of the above problems, and as a result, have at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-photosensitive layer on a transparent support. Silver genogen silver photographic light-sensitive material is stored in a patrone in a roll, and in a photographic film product stored in a packaging container, at least one of the photosensitive layers has a silver halide content of 70% or more of the total projected area. The silver halide emulsion contains a tabular silver halide emulsion having dislocation lines, and the silver halide color photographic light-sensitive material has a water content of not less than 2.0% and not more than 3.5% at 15 ° C. Above, at 25 ° C or less and relative humidity of 25% or more and 50% or less, it is possible to realize a photographic film product with excellent storage stability by storing it in a sealed container in a sealed state. O

 Hereinafter, details of the present invention will be described.

 First, details of the silver halide color photographic light-sensitive material according to the present invention will be described.

 In the silver halide color photographic light-sensitive material according to the present invention having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on a transparent support, at least one of the light-sensitive layers is required. One of the features is that the layer contains a plate-like silver halide emulsion in which 70% or more of silver halide grains of the total projected area have dislocation lines, and preferably a plate-like silver halide emulsion. However, 50% or more of the total projected area contains tabular silver halide grains having an average aspect ratio of 8 or more, or the variation coefficient of the particle size distribution in terms of circle diameter is 15% or more, 30% The following is preferred.

Tabular silver halide grains are crystallographically classified as twins. A twin is a crystal having one or more twin planes in one grain, and the classification of the twin morphology in silver halide grains is based on the report by Klein and Moiser, “P hot ₀ grap. Hishe K orrespondenz J 99:99, 100: 57. The tabular silver halide grains according to the present invention preferably have two or more twin planes parallel to each other in the grains. These twin planes are almost parallel to the plane having the largest area among the planes forming the surface of the plate-like particles (referred to as the main plane). A particularly preferred form in the present invention is a case having two parallel twin planes. In the silver halide emulsion according to the present invention, grains having 50% or more of the total projected area of the tabular grains have an average aspect ratio. The ratio is preferably 8 or more, more preferably 16 or more, and particularly preferably tabular silver halide grains having an average of 20 or more.

 The average aspect ratio of the tabular silver halide grains in the present invention can be adjusted to the above-mentioned desired range by appropriately selecting a production method known in the art.

Pur o

 In the present invention, the number of silver halide grains having two twin planes parallel to the main plane is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. Is particularly preferred. In the present invention, the average of the distance between two or more twin planes parallel to the main plane is 30 nm or less, preferably 1 nm or more, 2 O nm or less, more preferably 1 nm or more, and 120 A or less, 10 A or less. The above is particularly preferred.

 In the present invention, the intergranular distribution of the twin plane distance is preferably 40% or less, more preferably 30% or less.

The twin plane distance in the present invention is a factor affecting the supersaturation state at the time of nucleation, for example, gelatin concentration, temperature, iodine ion concentration, pBr, ion supply speed, stirring rotation speed, gelatin type, etc. Control by appropriate selection and combination of various factors 3 010987

8 You can In general, the higher the nucleation is in a supersaturated state, the narrower the twin plane distance can be. The details of the supersaturation factor can be referred to, for example, the descriptions in JP-A-63-92242 or JP-A-11-213637.

 The aspect ratio of silver halide grains can be obtained by the following formula by determining the grain size and grain thickness of each silver halide grain by the following method.

 Aspect ratio = particle size / particle thickness

 The tabular silver halide grain according to the present invention is preferably a tabular silver halide grain having two twin planes parallel to the main plane (111) having a main plane, and The diameter is preferably from 0.2 to 20 m, more preferably from 0.3 to 15 m, most preferably from 0.4 to 12 zm.

 In the present invention, the average particle diameter is an arithmetic average of the particle diameters ri. However, 3 significant figures and the least significant figure shall be rounded off, and the number of measured particles shall be indiscriminately 1,0000 or more. Here, the particle size r i is a diameter obtained by converting a projected image viewed from a direction perpendicular to the main plane of the tabular silver halide grains into a circular image having the same area. The grain size ri can be obtained by photographing silver halide grains with an electron microscope at a magnification of 10,000 to 70,000 and measuring the grain diameter on the print or the area at the time of projection.

In the present invention, the projected area and thickness of each grain for calculating the particle diameter ratio of the silver halide grain can be determined by the following method. A sample was prepared by coating a latex ball with a known particle size as an internal standard on a support and silver halide particles so that the main plane was oriented parallel to the substrate, and the particles were shadowed by carbon vapor deposition from a certain angle. After performing the attachment, the replica Make a charge. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the internal standard and the length of the shadow of the particle.

 In the present invention, in addition to the tabular grains according to the present invention, arbitrary ones such as a polydisperse emulsion having a wide particle size distribution and a monodisperse emulsion having a narrow particle size distribution can be used. The coefficient of variation of the particle diameter distribution in terms of circle diameter is preferably 15% or more and 30% or less, more preferably 15% or more and 25% or less. The average particle diameter and the standard deviation are determined from the particle diameter ri defined above. In the present invention, the tabular silver halide grains preferably contain silver iodide, and the average silver iodide content of the tabular silver halide grains is preferably 0.5 to 40 mol%. It is more preferably 0.5 to 30 mol%, and further preferably 1.0 to 25 mol%. The silver iodide content of the silver halide grains is determined by the EPM A method (Electron PRobeMicroAnalyzer method).

 In the present invention, the average silver iodide content on the surface of the silver halide grains is preferably from 0.5 to 20 mol%, more preferably from 1 to 15 mol%. The surface silver iodide content of the silver halide grains referred to in the present invention means the iodide content in the silver halide phase up to a depth of 50 A from the surface of the silver halide grains including the surface of the silver halide grains. It refers to the silver halide content.

In the tabular silver halide emulsion according to the present invention, at least one photosensitive layer contains a tabular silver halide emulsion having 70% or more of the total projected area of silver halide grains having dislocation lines. It is characteristic. The form of the dislocation lines introduced into the silver halide grains can be appropriately selected. For example, a dislocation line that exists linearly in a specific direction of the crystal orientation of the particle or a dislocation line that is bent can be selected. Furthermore, it exists over the entire particle or only in a specific part of the particle, for example, a form in which dislocation lines exist only in the fringe portion (outer peripheral portion) of the particle, or only in a main plane. Then, it is also possible to select from a mode in which dislocation lines exist or a mode in which dislocation lines exist intensively near the vertex. In the tabular silver halide grains according to the present invention, dislocation lines are preferably present at least in the fringe portions of the grains, and preferably have 10 or more dislocation lines in the fringe portion, and more preferably 20 or more. More preferably, it is.

 The dislocation lines of silver halide grains are, for example, JF H amilton, P hot o. S ci. Eng. 1 1 (1967) 57, T. S hioz aw a, J. S o c. P hot S ci. Japan 35 (1972) 213 can be observed by a direct method using a transmission electron microscope at low temperature. In the tabular silver halide grains according to the present invention, 50% of the grains preferably have 10 or more dislocation lines in the fringe portion, and more preferably 70% or more, in the number ratio of grains. Further, the number ratio of tabular silver halide grains having fringe dislocation lines is preferably 50 to 100% by number, more preferably 60 to 100% by number, and more preferably 70 to 100% by number. More preferred.

The phrase "tabular silver halide grains having dislocation lines in the fringe portion" as used in the present invention means that there are at least 10 dislocation lines per grain near the outer periphery, near the ridge, or near the apex of the tabular grains. . Specifically, the fringe part is a line segment that connects the center of the main plane of the tabular grain (the center of gravity when the main plane is regarded as a two-dimensional figure) and the vertex, observing the tabular grain perpendicular to the main plane. Where L is the center of each vertex Refers to the area outside the figure connecting the points whose distance from is 0.50 L.

 In the present invention, as a method for introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution by double jetting, or iodide Known methods such as a method of adding silver fine particles, a method of adding only a solution containing iodide ions, and a method of using an iodide ion releasing agent as described in JP-A-6-11781 Can be used to form dislocations that originate dislocation lines at desired locations. Among these methods, a method of adding an aqueous solution containing iodide ions and a water-soluble silver salt solution in a double jet, a method of adding silver iodide fine particles, and a method of using an iodide ion releasing agent are preferable. The iodide ion releasing agent referred to in the present invention is a compound which releases iodide ion by reacting with a base or a nucleophile represented by the following general formula (2).

 General formula (2)

 R—I

In the general formula (2), R represents a monovalent organic group. R is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, It is preferably a arylsulfonyl group or a sulfamoyl group. R is preferably an organic group having 30 or less carbon atoms, more preferably 20 or less, and even more preferably 10 or less. R preferably has a substituent, and the substituent may be further substituted with another substituent. Preferred examples of the substituent include a halide, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, and an aryloxy group. Xycarbonyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, alkoxy group, aryloxy group, amino group, acylamino group, レ イ reido group, urethan group, sulfonylamino group, sulfinyl group, amide phosphate Group, alkylthio group, arylthio group, cyano group, sulfo group, carboxyl group, hydroxy group, nitro group and the like.

 Preferable examples of the iodine ion releasing agent represented by the general formula (2) include o-alkanes, o-alcohols, eodo-rubonic acids, e-o-amides and derivatives thereof, e.g., o-amides, o-alcohols and the like. The derivatives of the above are more preferred, and the amides substituted with a heterocyclic group are still more preferred, and the most preferred example is (r-doacetamido) benzenesulfonate.

 In the present invention, when an iodide ion releasing agent is reacted with a nucleophile to release iodide ions, examples of the nucleophile include hydroxide ion, sulfite ion, thiosulfate ion, sulfinate, and carboxylate. , Ammonia, amines, alcohols, ureas, thioureas, phenols, hydrazines, sulfides, hydroxamic acids, etc .; hydroxide ions, sulfites, thiosulfate ions, Sulfinates, carboxylates, ammonia and amines are preferred, and hydroxide ions and sulfite ions are more preferred.

 The silver halide emulsion according to the present invention contains at least one kind of a polyvalent metal atom, a polyvalent metal atom ion, a polyvalent metal atom complex or a polyvalent metal atom complex ion inside or on the surface of silver halide grains. Is preferred.

The polyvalent metal atom, the polyvalent metal atom ion, the polyvalent metal atom complex or the polyvalent metal atom complex ion includes Fe, Co, Ni, Ru Rh P d ヽ R e O s, I r, Pt, Mg, Al, Ca, Sc, Ti, V, Cr, MnCu, Z n, G a, G e, As, S e, S r, Y, Mo, Z r, N b, C d, In, S n, S b, B a, L a, W, A u, Hg, Tl, Pb, Bi, Ce and U etc. Metal atoms, ions, complexes thereof from the 3rd to 7th period (most commonly the 4th to 6th period) of the periodic table. At least one selected from salts containing these (including complex salts) and other compounds containing these can be used, but it is preferable to select from single salts or metal complexes.

 When a metal complex is selected, a six-coordinate complex, a five-coordinate complex, a four-coordinate complex, and a two-coordinate complex are preferable, and an octahedral six-coordinate complex and a planar four-coordinate complex are more preferable.

Ligands for constituting the _{complex, CN-, CO, N0 2 -} , 1, 10- Fuwenan Toro Li down, 2, 2 'single Bibirijin, SO ₃ -, ethylenediamine, NH _3, pyridine emissions, H _{2 0, NC S-, NCO- 0 3} , S 0 4 2 - OH- N 3-, S 2 one, F-, C 1 one, B r-, I-, etc. can be used.

 In order to incorporate a polyvalent metal into the silver halide emulsion used in the present invention, the following known techniques can be applied.

For example, BH Carroll, "Iridium Sensitization, AL iterature Review", Photographic Science and Engineering, Vol. 24, No. 6, 1980 December 1Z December, 265-267, U.S. Pat. 95 1, 933, 2, 628, 167, 3, 687, 676, 3, 761, 267, 3, 890, 154, 3, 90 1 No. 3, 911, No. 3, 901, 713, No. 4, 173, 483, No. 4, 269, 927, No. 4, 413, 055, No. 4, 477, 56 No. 1, No. 4, 581, 327, No. 4, 643, 965, No. 4, 806, 462, No. 4, No. 828, 962, No. 4, 835, 093, No. 4, 902, 611, No. 4, 981, 780, No. 4, 997, 751, No. 5, 057 No. 5, 402, No. 5, 134, 060, No. 5, 153, 110, No. 5, 164, 292, No. 5, 166, 044, No. 5, 204, 234 No. 5,166,045, 5,229,263, 5,252,451, 5,252,530, EP 0244184, 0488737 No. 0488601, No. 0368304, No. 0405938, No. 0509674, No. 0563946, Japanese Patent Application No. 2-249588, WO 93/02390, etc. can be applied. . In addition, U.S. Patent Nos. 4,847,191, 4,933,272, 4,981,781, 5,037,732, 937,180, 4,945, Nos. 035, 5, 112, 732, EP O 0509674, EP 05 13738, WO 91 10166, 92Z 16876, Doit Patent 298, 320, U.S. Patent No. The techniques described in 5, 360, 712 and 5, 024, 931 can be applied.

 Item 36736, Item 3736, which is an easy-to-understand explanation of the criteria for selecting shallow electron trapped pumps, is described in ResealcDiscslosure (hereinafter abbreviated as RD), Volume 367, January 1994, January 1994.

 The silver halide emulsion according to the present invention is preferably silver bromide, silver iodobromide, or silver iodobromochloride, and particularly preferably silver iodobromide or silver iodobromochloride. The silver chloride content is preferably from 0 to 50 mol%, more preferably from 0 to 30 mol%, even more preferably from 0 to 10 mol%.

A dispersion medium which can be preferably used for the silver halide emulsion according to the present invention. And gelatin and hydrophilic colloids. No. 1 is generally used as a gelatin having an average molecular weight of about 100,000, an acid-treated gelatin, an acid-treated gelatin, an oxidized gelatin, a Bull. Soc. S ci. P hot o. 6. Enzyme-treated gelatin as described in P30 (1966) can be preferably used. Examples of hydrophilic colloids include gelatin derivatives, proteins such as graft polymers of gelatin and other macromolecules, albumin and casein; hydroxyxethyl cellulose, carboxymethyl cellulose and cellulose sulfate esters. Derivatives such as cellulose derivatives, sodium alginate, starch derivatives, etc .; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-1 N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazo-1 And various kinds of synthetic hydrophilic high molecular substances such as mono- or copolymers such as poly (vinyl virazole).

 In the production of the silver halide emulsion according to the present invention, it is preferable to provide one or more desalting steps during grain formation. Here, the desalting step is to wash the silver halide emulsion with water to remove soluble salts. The desalting step can be performed by referring to Research Disclosure (hereinafter abbreviated as RD), No. 17643, Item II, using inorganic salts, anionic surfactants or anionic polymers (for example, polystyrenesulfonic acid). It can be preferably carried out by the flocculation method used. The desalting step is preferably performed at a time point of less than 10% by volume, more preferably at a time point of less than 5% by volume, based on the volume after growth of the silver halide grains.

The silver halide emulsion according to the present invention may be subjected to reduction sensitization. The reduction sensation is achieved by adding a reducing agent to the aqueous solution of protective colloid in which silver halide grains grow. Alternatively, the aqueous solution of the protected colloid in which silver halide grains are grown is subjected to a low pAg condition of PAg 7.0 or less, or a high pH condition of pH 7.0 or more, and silver halide grains are used. Can be applied by aging or grain growth. These methods may be appropriately combined.

 Various methods well known in the art can be used for forming silver halide grains in the production of the silver halide emulsion of the present invention. That is, a single-jet method, a double-jet method, a triple-jet method, a method of supplying fine silver halide particles, or the like can be used in any combination. In addition, a method of controlling pH and pAg in a liquid phase in which silver halide is formed in accordance with the growth rate of silver halide can also be used. The formation of silver halide grains is preferably performed under conditions close to the critical growth rate.

 In preparing the silver halide emulsion of the present invention, a silver halide solvent known in the art can be used.However, if possible, the use of the silver halide solvent during the formation of base tabular grains is not required. However, it is better to avoid it except ripening after nucleation.

 For the production of the silver halide emulsion of the present invention, any of an acidic method, a neutral method and an ammonia method can be used, but the acidic method or the neutral method is preferred. In the production of the silver halide emulsion of the present invention, halide ions and silver ions may be mixed at the same time, or one may be mixed in the presence of one. Also, in consideration of the critical growth rate of silver halide crystals, halide ions and silver ions can be added sequentially or simultaneously while controlling pAg and pH in the mixing vessel. In any step of silver halide formation, the halogen composition of the silver halide grains may be changed by using a conversion method.

In the production of the silver halide emulsion according to the present invention, at least a part of the growing step In the above, it is preferable to carry out a concentration operation of the silver halide emulsion by an ultrafiltration method. In the case of producing a tabular emulsion having a high aspect ratio such as the silver halide emulsion of the present invention, a dilution environment is preferable. Therefore, the ultrafiltration method is preferably applied in order to improve productivity. When the concentration operation of the silver halide emulsion is carried out by ultrafiltration, a silver halide emulsion production facility disclosed in JP-A-10-339923 can be preferably used.

 In the production of the silver halide emulsion of the present invention, the conditions other than those described above are described in JP-A-61-6643, JP-A-61-14630, JP-A-61-112142, JP-A-62-157024, and JP-A-62-157024. — No. 18556, No. 63—92942, No. 63—151 618, No. 63—163451, No. 63—220238, No. 63—311244, No. I and III of RD 38957, RD40 145 Appropriate conditions can be selected with reference to the XV section of the above.

 The silver halide emulsion having the above specific structure according to the present invention can be subjected to chemical sensitization according to a known method.

 The silver halide color photographic light-sensitive material according to the present invention preferably contains a compound represented by the following general formula (1), and in particular, a silver halide color photographic light-sensitive material containing a tabular silver halide emulsion. This is preferable for a photographic film product in which is stored in a sealed container in a sealed form, because the rise in capri concentration during long-term storage can be suppressed.

In the general formula (1), represents a hydrogen atom or an alkyl group. Q represents a nonmetallic atomic group necessary to form a 5- to 7-membered ring together with N and C = 0. A and B each represent a copolymerizable ethylenically unsaturated compound. x, y, and z each represent mol%, and 10 ^ x ^ 100, 0≤y≤9 Os 0≤z≤90. Also, the number average The molecular weight is between 200 and 200,000.

Examples of the ethylenically unsaturated compounds represented by A and B in the general formula (1) include acrylic esters, methacrylic esters, acrylamides, methacrylamides, aryl compounds, vinyl esters, and the like. Examples include ters, vinyl esters, vinyl heterocyclic compounds, styrenes, maleic esters, fumaric esters, itaconic esters, crotonic esters, and olefins. Specifically, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-cyanoethyl acrylate, N— (/ 3— Dimethylaminoethyl) acrylate, benzylacrylate, cyclohexylacrylate, phenylacrylate: methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate Relate, 3-sulfopropylmethacrylate: arylbutyl ether, arylvinyl ether: methyl vinyl ether, butyl vinyl ether: methoxyl ethyl vinyl ester, 2-hydroxyl Tyl vinyl ether, (2- Dimethylamino ether) vinyl ether, vinyl phenyl ether, vinyl chlorophenyl ether, acrylamide, methacrylamide, N-methylacrylamide, N- (1,1-dimethyl-13-oxobutyl) acrylamide, N— (1,1-Dimethyl-3-hydroxybutyl) acrylamide, N, N—Dimethylacrylylamide, acryloylhydrazine, N—Methoxymethylmethacrylamide, N— (1,1, Dimethyl 1-Hydroxybutyl) methacrylamide, N-hydroxyquinmethylacrylamide: vinyl pyridine, N-vinyl imidazole, N-vinyl carbazole, vinyl thiophene: styrene, Methyl styrene, p-acetoxy styrene, p-methyl styrene: p-vinyl benzoic acid, P-methyl methyl benzoate: crotonamide, butyl crotonate, glycerin monotonate: methyl vinyl ketone, phenyl Rubinyl ketone: ethylene, propylene, 1-butene, dicyclopentadiene, 4-methyl-111-hexene, 4,4-dimethyl-11-pentene: methyl itaconate, ethyl itaconate, getyl itaconate: methyl sorbate, methyl sorbate, Ethyl maleate, butyl maleate, dibutyl maleate, octyl maleate: ethyl ethyl fumarate, dibutyl fumarate, octyl fumarate: halogenated olefins such as vinyl chloride, vinylidene chloride, isoprene: acrylonitrile, methacryloyl Unsaturated nitriles such as nitriles is there.

 Preferred specific examples of the compound represented by the general formula (1) include, but are not limited to, the following. The numerical value in parentheses of each copolymer is the mole composition ratio.

 P—1: Poly (N-vinylpyrrolidone)

P-2: N-vinylpyrrolidone / vinyl alcohol copolymer (80/20) P-3: N-vinylpyrrolidone / novinyl alcohol copolymer (70Z30) P-4: N-vinylpyrrolidone / vinyl acetate copolymer Combined (70/30) P-5: N-vinylpyrrolidone / acrylic acid copolymer (90/10)

P-6: N-Vinylpyrrolidone Z2-Hydroxyshetyl acrylate copolymer

 (70/30)

P-7: N-vinylpyrrolidone-no-acrylamide copolymer (80-20) P-8: N-vinylpyrrolidone-no-acrylamide copolymer (60/40) P-9: N-vinylpyrrolidone / Dimethyl acrylamide copolymer (70/30)

 P-10: N-vinylpyrrolidone / vinylacetamide copolymer (70/30) P-11: N-vinylpyrrolidone Z vinyl acetate Z vinyl alcohol

 Copolymer (60/30/10)

 5 P—12: N—Vinylpyrrolidone 2—Hydroxyshetyl acrylate /

 Vinyl acetate copolymer (70/20/10)

 P-13: Poly (N-vinyloxazolidone)

 P-14: Poly (N-vinylpiperidone)

 P-15: Poly (N-vinyl succinimide)

10 P—16: Poly (N—vinyl glutarimide)

 P-17: N-vinylpyrrolidone / 2-methoxyl acrylate copolymer

 (70/30)

 P-18: N-vinylpyrrolidone / methylvinyl ether copolymer

 (80/20)

 15 P-19: N_vinylpyrrolidone / N-vinylpyridone / 2-hydroxyethyl acrylate copolymer (50/30/20)

 P-20: N-vinyl-s-caprolactam Z-acrylamide copolymer

 (60/0)

 In the present invention, the compound represented by the general formula (1) has a number average molecular weight of 200 to 200,000.

The amount of addition is not particularly limited, but preferably includes at least 1. Omg / m ^{2 of the} compound represented by the general formula (1) in the photosensitive layer. 1. OmgZm 2 or more, 500 m gZm ² or less is more preferable, 1.OmgZm ² or more, 500 m gZm ² or less is particularly preferred.

 The silver halide color photographic light-sensitive material for photography according to the present invention has a constitution in which at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-light-sensitive layer are respectively provided on a transparent support. However, if necessary, an antihalation layer, one yellow filter layer, an intermediate layer, and the like may be appropriately provided. Further, the protective layer according to the present invention may be composed of two or more layers as necessary. In the silver halide color photographic light-sensitive material for photography of the present invention, the following components other than those described above can be appropriately selected and used.

 In the silver halide color photographic light-sensitive material for photography according to the present invention, the silver halide emulsion used in each photosensitive silver halide emulsion layer is Research Disclosure (hereinafter abbreviated as RD) No. 308 119. Items described in each item can be used.

 The places to be described are shown below.

 (Items) (RD 308 1 19 page)

 Iodine composition 993 I-1 A

 Production method 993 I-A and 994 E Crystal habit Normal crystal 993 I-A

 Crystal habit Twin crystal 993 I—A term

 Construction 993 I-A Section A

 Halogen composition uniform 993 I—B term

 Non-uniform halogen composition 993 I—B term

 Halogen converge 3 994 I-C

Halogen substitution 994 I-C 994 I—D

 Monodisperse 995 I-F term

 Solvent addition 995 I-F

 Latent image formation position Surface 995 I-G

 Latent image formation position Inside 995 I-G section

 Applicable silver halide photographic photosensitive material negative 995 I-H section

 Positive (including internal capri particles) 995 I-H

 995 I-J with mixing emulsion

 Desalination 995 II-A Section A

 In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and photosensitization is used. Additives used in such a process are described in RDN 0.17643, No. 18716 and No. 308119. The places to be described are shown below.

 [Item] [RD 3081 page 19]! : RD 17643] [RD 187 16] Chemical sensitizer 996 ΙΠ—Section A 23 648 Spectral sensitizer 996 IV—A-A,

 B, C, D, 23—24 648-649 H ヽ I, J

 Supersensitizer 996 IV—A—E, J

23-24 648-649 Power pre-inhibitor 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographic silver halide color photographic materials which can be used in the present invention. Additives are also described in the above RD. The relevant sections are described below. [Items] [RD3081 page 19] “RD1 7643” [RD187 16] Anti-turbidity agent 1002VII-I 25 25 650 Dye image stabilizer 1001 VI I _J 25

 Brightener 998 V 24

 UV absorber 1003 VII section I,

 XI I C Section 25 26

 Light absorber 1003 VII 25 26

 Light scattering agent 1003 VII

 Filter dye 11000033VVIIIII 25-26

 Binder 11000033 IIXX 26 65 1 Static inhibitor 1006X1 II 27 650 Hardener 1004X 26 65 1 Plasticizer 1006X11 27 650 Lubricant 1006 XII 27 650 Activator 'Coating aid 1 005X1 26-27 650 Matting agent 1007XVI

 Developer (contained in silver halide color photographic material for photography)

 100 1 XXB

 Various couplers can be used in the photosensitive layer according to the present invention, and specific examples thereof are described in RD. The relevant sections are described below.

[Item] [Page of RD 308 1 19] [RD 17643] Yellow coupler 1001VII—D section VIIC to G section Magenta coupler 100 1 VII—D section VIIC to G section Cyan coupler 100 1 VII—D section VIIC to G Colored scarf 1002 VII—G section VIIG section

 D I R coupler 100 1 VII—F section VIIF section

 BAR coupler 1002 VII—F

 Release of other useful residues 1001 VII—Section F

 Coupler

 Alkali-soluble coupler 100 Section 1VII-E

 Each of the above additives can be added by a dispersion method described in RD308119 XIV.

 The silver halide color photographic light-sensitive material for photography of the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD3081 19VII-K.

 The silver halide color photographic light-sensitive material for photography of the present invention can have various layer constitutions such as a forward layer, a reverse layer, and a unity constitution described in the aforementioned RD3081 19 VII-K.

For developing processing of the silver halide color photographic light-sensitive material for photography of the present invention, for example, T. H., James, Theory of the Photographic Process, 4th edition (T heheory of T he P hotgraphic Process Forth E) dition), pp. 291-334 and Journal Off, The American American Chemical Society, Vol. 73, No. 3, pp. 100 (1951). Use developer Can. Further, development processing can be carried out by a conventional method described in RD 17643, pp. 28-29, RD 18716, 615 and RD 308 119 XIX.

 Next, the packaging container and the packaging method according to the present invention will be described.

 In the photographic film product of the present invention, the silver halide color photosensitive material according to the present invention is used at a water content of 2.0% or more and 3.5% or less at a temperature of 15 ° C or more and 25 ° C or less. It is characterized by being housed in a sealed container in a sealed state under an atmosphere having a relative humidity of 25% or more and 50% or less.

 In the present invention, there is no particular limitation on the method of controlling the moisture content of the silver halide photographic light-sensitive material at the time of packaging to 2.0% or more and 3.5% or less. The method of adjusting the drying conditions or the environmental conditions (temperature and humidity) at the time of winding, and adjusting the amount of the hardener added to the binder (specifically, gelatin) used to obtain the desired water content. Rate can be achieved.

 The water content of the silver halide color photographic light-sensitive material specified in the present invention is, for example, 11-1 ^ 100 DIGITAL TAL MOISTURE manufactured by Infrared Moisture Analyzer (Chinoichi Co., Ltd. (111) ^ 0). METER). In the present invention, a packaging container for storing a silver halide color photographic light-sensitive material having the above-described structure and having a water content of 2.0% or more and 3.5% or less will be described.

As one form of the packaging container according to the present invention, Poriorefui emissions based Ru sealed resin container name from resin or moisture ^{permeability, 20. 0 g / m 2 -} 24 h (40 ° C - 90% RH) or less of moisture It is preferably a bag. In addition, the moisture permeability referred to in the present invention can be measured according to a method specified in JISZ02080. The sealed resin container made of the polyolefin resin according to the present invention refers to a silver halide color photographic light-sensitive material which is slit into a band, usually 35 mm in size, and cut into a predetermined length. After being wound around a spool and stored in a metal cartridge in a light-shielded state, it is a container made of an olefin resin consisting mainly of a cylindrical tube and a cap. Examples of the polyolefin-based resin include homopolymers of olefins such as ethylene and propylene and copolymers with different olefins.

 After putting in a plastic container in this way, put it in a plurality of thermoplastic bags with a design print, or put a 13.5 size film with a pat opening in the resin container, then remove the design print. Boxed items are sold as single or multiple shrink films.

Next, a moisture-proof bag having a moisture permeability of 20.0 g / m ² · 24 h (40 ° C./90% RH) or less will be described.

As the moisture-proof bag according to the present invention, it is preferable to use a thermoplastic resin film material, which satisfies the condition of moisture permeability 20.0 g / m ² ■ 24 h (40 ° C.-90% RH) or less. There is no particular limitation as long as it is a thermoplastic resin film material (eg, a new development of functional packaging materials. Thermoplastic resin film described in Toray Research Center Co., Ltd.).

As an example of the thermoplastic resin film material used in the present invention, a material containing at least one inorganic vapor-deposited layer as described in JP-A-6-93502 can be mentioned. In a preferred embodiment, a transparent thermoplastic resin film is laminated on the upper side or one side via the inorganic vapor-deposited layer, and at least one innermost layer is formed of a thermoplastic resin. These inorganic vapor deposited films are thin film handbooks p 879-901 (Japan Society for the Promotion of Science), vacuum technology handbooks 502-? 509, 612, 810 (Nikkan Kogyo Shimbun), and the vacuum handbook revised editions p132-pl34 (ULVAC Japan Vacuum Technology K. K).

For _{example, C r 2 0 3, S} i x O y (x = l, y = l. 5~2. 0)ヽ _{T a 2 0 3, Z r} N, S i C, T i C, PSG, S i ₃ N "single crystal S i, Amorufasu S iヽW, A 1 ₂ 0 ₃ or the like is used.

 Examples of the thermoplastic resin film used as a base material of the transparent moisture-proof material include ethylene tetrafluoroethylene copolymer (ETFE), high-density polyethylene (HDPE), biaxially oriented polypropylene (0PP), polystyrene (PS), and polymethylmethacrylate. Film materials used for general packaging films such as RELAT (PMMA), biaxially stretched nylon 6, polyethylene terephthalate (PET), polycarbonate (PC), polyimide, and polyether styrene (PES) Can be used.

 Examples of the method for producing a vapor-deposited film include a general method described in Vacuum Technology Handbook and Packaging Technology Vol. 29—No. 8, for example, a resistance or high-frequency induction heating method, an electron beam (EB). ) Method, plasma (PCVD), etc. The thickness of the deposited film is preferably in the range of 400 to 2000 A, more preferably in the range of 500 to 180 OA.

As the thermoplastic resin film used through the vapor-deposited film sheet, a polymer film used as a general packaging material (for example, a polymer film described in Toray Research Center Co., Ltd., a new development of functional packaging materials) is used. Some low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density poly Ethylene (LLDPE), medium density polyethylene, unstretched polypropylene (CPP;), stretched polypropylene (0PP), stretched nylon (0Ny), polyester (PET), cellophane, polyvinyl alcohol (PVA), stretched vinylon (0V) ), Ethylene monovinyl acetate copolymer (EVOH), vinylidene chloride (PVDC) and the like can be used.

 As the thermoplastic resin film, a multilayer film formed by co-extrusion with a different kind of film or a multilayer film formed by laminating at different stretching angles can be used as required. Furthermore, it is of course possible to combine the density and molecular weight distribution of the film used to obtain the required physical properties of the packaging material. As the innermost thermoplastic resin film, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE) manufactured using a metallocene corrosion medium, linear low-density polyethylene (LLDPE) ), And films using a mixture of these films and high-density polyethylene (HDPE) films are used.

 When the inorganic vapor-deposited layer is not used, the above-mentioned thermoplastic resin film may be used alone, if necessary, or may be used by laminating two or more kinds of films. For example, CP PZOP P, PET / OP PZLDP E, Ny / OPP / L DP E, CPP / OPP / EV OH, Saran UB / LLDP E (where Saran UB is vinylidene chloride / acrylic acid manufactured by Asahi Kasei Corporation) A biaxially stretched film made from an ester-based copolymer resin is shown.) Κ-ΟΡ / Ρ Ρ ^ Κ-ΕΤ ΕΤ / L LDP E, K-Ny / EVA (where K is coated with vinylidene chloride resin) Etc.) are used.

In the moisture-proof bag according to the present invention, a light-shielding substance can be used if necessary. Carbon black is generally used as the substance. Among carbon blacks, the content of free yeolite is 200 ppm or less, the average particle diameter is 10 to 120 μm, the pH is 6.0 to 9.0, and the average particle diameter is 10 to L; Particularly preferred are furnace blacks having an oil absorption of 60 m1 / 100 g or more and a volatile component of 3.0% or less.

 The thickness of the thermoplastic resin film used in the present invention is from 30 to 400 m, preferably from 40 to 200 m, more preferably from 60 to 200 m. If it is less than 30 m, the moisture-proof function is reduced and the oxygen permeability is increased, making it difficult to maintain the performance of the photographic material. On the other hand, if the thickness exceeds 400 m, the thickness becomes too large to be the same as that of a conventional resin container, resulting in excessive packaging, and at the same time, low environmental suitability.

 In the photographic film product of the present invention, the atmosphere when the silver halide color photosensitive material according to the present invention is stored in the above-described resin container or moisture-proof bag is at least 15 ° C and at least 25 ° C. C and a relative humidity of 25% or more and 50% or less, and preferably a relative humidity of 35% or more and 50% or less. When the relative humidity is 25% or more, there is no effect on the coating properties of the silver halide color photographic light-sensitive material, and the silver halide grains are stressed due to shrinkage of the coating due to excessive drying. Capri that occurs can be prevented. In addition, when the relative humidity is 50% by mass or less, it is possible to prevent the occurrence of fog or the like due to humidity under airtightness during storage.

 Example 1

 《Production of photographic film products》

 [Production of photographic film product 1]

[Preparation of Sample 101] On a triacetylcellulose film support with a thickness of 125〃 ^ 1 and a width of 1.25 m with an undercoat layer, a slide hopper was constructed in such a manner that each layer with the composition shown below was formed sequentially from the support side. After the simultaneous multi-layer coating was performed using a mold coater, it was dried, laminated in a roll shape and wound up. The winding was performed in an atmosphere of 18 ° (40% RH) to prepare Sample 101 which is a silver halide color photographic light-sensitive material for photography.

The amount of each material added below are expressed in grams per 1 m ^2. However, silver halide and silver colloid were converted to the amount of silver, and the sensitizing dye (indicated by SD) was shown in moles per mole of silver.

(First layer: Anti-halation layer) (gZm ² ) Black colloidal silver A (Total iron and copper content 0.40 ppm) 0.13 U V- 1 0.30

CM— 1 0. 1 1

O I L-10.22 Gelatin 1.28

(2nd layer: middle layer)

 O I L-3. 0.267 Gelatin 0.89 (3rd layer: low-sensitivity red-sensitive layer)

 Silver iodobromide emulsion a 0.29 Silver iodobromide emulsion c 0.23

S D— 1 39 X 10

S D- 2 6 0 X 10 S D- 3 2.89 X 10

C-1 10.375 c c-1 0. 064

D— 1 0. 0 16 A S-2 0. 002

O I L-20.229 Gelatin 0.98 (4th layer: middle-sensitivity red-sensitive layer)

 Silver iodobromide emulsion b 0.10 Silver iodobromide emulsion d 0.30

S D— 1 4.77 X 10

S D— 2 6.55X 10

S D— 3 3.13 X 10

C-1 0.200 C C-1 0.040

D— 1 0. 022

D-3 0.002

A S— 2 0.001

O I L-2 0.130 Gelatin 0.64

(Fifth layer: high-sensitivity red-sensitive layer)

Silver iodobromide emulsion d 0.09 Silver iodobromide emulsion g 0.34 SD—1 3.68 X 10 SD—2 5.06 X 10 S D- 3.2.42 X 10 C—1.0.054 C- 20.040 CC-1 0.018 D- 30. 003 AS-2 0.001 OIL-2 0.058 Gelatin 0.55

(6th layer: middle layer)

 A S-1 0.17

0 I L-1 0.22 Gelatin 0.89 (7th layer: low-sensitivity green photosensitive layer)

 Silver iodobromide emulsion b 0.19 Silver iodobromide emulsion c 0.10

S D-4 7.00 X 10

S D— 5 7.25 X 10 S D-6 9.1 X 10

M— 1 0. 285

CM—1 0.087

D—2 0. 003 D— 3 0. 001

A S-2 0.001

X- 2 0.07

A S—3 0.034 O I L-1 0. 340 Gelatin 1.0 1 (8th layer: middle-sensitive green photosensitive layer)

 Silver iodobromide emulsion c 0.09 Silver iodobromide emulsion d 0.3 1 S D— 4 8 15 X 10

S D— 5 8 45 X 10

S D- 6 06 X 10

M— 1 0. 057

CM— 1 0. 030 D— 2 0. 0 1 1

D- 3 0.001

A S-2 0.001

X- 2 0.0.17

A S— 3 0. 009 0 I L-1 0. 20 1

0 IL-3 0.049 Gelatin 0.92 (9th layer: high-sensitivity green photosensitive layer) Silver iodobromide emulsion b 0.08 Silver iodobromide emulsion f 0.38 S D-4 51 3 X 10 S D- 5 1 18 X 10 SD- 6 3 97 X 10 S D- 9 2 2 X 1 0 M—1 0.0.58 CM—1 0.0.29 D—3 0.00 1 AS-2 0.00 1 X-2.0.0 1 AS-3 0.0.07 OIL- 10.10 Gelatin 0.990 (Layer 10: One layer of yellow filter

 Yellow color silver 0.06 AS-1 0.06 0 IL-10.0.08 Gelatin 0.88 (first layer: low-sensitivity blue-sensitive layer)

Silver iodobromide emulsion b 0.12 Silver iodobromide emulsion d 0.16 Silver iodobromide emulsion e 0.12 S D- 7 5 86 X 10

S D— 8 1 53 X 1 0

Y— 1 1. 1 0

D— 3 0.002 A S-2 0.004

O I L-1 0.000 Gelatin 2.05 (1st 2nd layer: high-sensitivity blue-sensitive layer)

 Silver iodobromide emulsion h 0.29 SD-7 3.30 X 10

S D- 8, 8, 59 X 10

Y— 1 0. 1 00

A S-2 0. 0 0 1

D-4 0 .0 5 O I L-1 0 .0 6 7

O I L-3 0.160 Gelatin 0.76 (1st 3rd layer: 1st protective layer)

 Silver iodobromide emulsion i 0.22 U V-10.3 8

U V-2 0. 0 5

U V-3 0.0 3

X-1 0. 04 AF-600003 Gelatin 092 (14th layer: 2nd protective layer)

PM-1 0.13 PM-20.037 WAX-10.02 SU-10.009 Gelatin 0.55 In addition to the above compositions, coating aids SU-2, SU-3 , Dispersing aid SU-4, Viscosity modifier V_l, Stabilizer ST-1, Calcium chloride, Inhibitor AF-3, AF_4, AF-5, AF-7, Hardener H-1, H-2 And the preservative A se-1 was added as appropriate. The total dry film thickness of the blue light-sensitive layer of Sample 101 prepared above was 3.50 μm, the silver content of the high-sensitivity blue light-sensitive layer of the twelfth layer, Z gelatin mass ratio was 0.53, and blue total silver of the photosensitive layer is 0. 68 gZm ^2.

 The characteristics of each silver iodobromide emulsion used in the preparation of Sample 101 are shown in the table below. The average grain size of silver iodobromide emulsions c, d, e, i, g, and h is the diameter (average value) of a circle equivalent to the same projected area. And i are represented by the length of one side of the cube (average value).

 The following silver iodobromide emulsions were prepared so as to have the following characteristics by adjusting the grain growth conditions according to the method described in Examples of JP-A-10-123640.

/ o Silver iodobromide emulsion Average grain size Average iodine content Average aspect ratio Dislocation line (βτ) (mol%) (Average grain size Ζ thickness) Presence Silver iodobromide emulsion a 0.27 2. 0 frn *. Silver iodobromide emulsion b 0.28 2.0 No silver iodobromide emulsion c 0.6.1 3.1.43.43 No silver iodobromide emulsion d 0.89 3.7 6.10 ^ rn *-silver iodobromide emulsion e 0.95 8. 0 3.07 no silver iodobromide emulsion ί 1. 3 3.9 8.76 no silver iodobromide emulsion g 1.50 3.1 8.60 nt.Silver iodobromide h 1.23 7.9 8.85

Silver iodobromide emulsion i 0.03 1.9 nt.

For each emulsion except silver iodobromide emulsion i, after adding each of the above sensitizing dyes, sodium thiosulfate, chloroauric acid, potassium thiocyanate, etc. were added to optimize the relationship between capri-sensitivity. Was subjected to chemical sensitization.

 The details of the compounds used for preparing Sample 101 are described below.

The water content of the sample 101 was measured with an IR-AM100 DIGITAL MOISTURE METER manufactured by Chino Corporation and found to be 2.8%.

C-1 2

CM— 1

D-4

AS-1

AS-1

AS— 2

AS -3

OIL— 2 OIL— 3

 Liquid paraffin

UV-3 H ₉ C ₄ OOC (CH ₂ ) ₈ COOC ₄ H ₉

UV-3

V-1

 n: degree of polymerization

 Ase-1 (a mixture of the following three components)

,,

C to S CH ₃

(Component A) (Component B) (Component C) Component A: Component B: Component C = 50: 46: 4 (molar ratio)

H-1

CH ₂ = CHS_〇 _{2 - CH 2 CONHC 2 H 4} NHCOCH 2 -S0 2 CH = CH 2

H-2

 ONa

 N people N

 CI Person N CI

X— 2 Α "Λ

H ₂₉ C ₁₄ OOCH ₄ C ₂ — ^-C ₂ H ₄ COOC ₁₄ H ₂₉

-1 H

-1 H

 o 丫 u

 HN-

NHCONH ₂

SU-2 Na0 ₃ Sv ^c OOCH ₂ (CF ₂ CF ₂ ) ₃ H

, COOCH ₂ (CF ₂ CF ₂ ) ₃ H CH ₂ COOCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉

 SU-3

† HCOOCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉

S0 ₃ Na ccl-

 x: y: z = 3: 3: 4

 n: degree of polymerization

(Production of package)

 Sample 10 1 prepared above was slit to a width of 35 mm in an environment of 23 ° (: 45% RH), cut into 1 35 size standard 24 shots, punched, wound on a spool, and stored in a metal cartridge This was stored in a transparent polyethylene resin can, and then sealed with a polyethylene lid to produce Photographic Film Product 1.

[Production of photographic film products 2 to 11] In the preparation of the above photographic film product 1, the photographic film products 2 to 11 were prepared in the same manner except that the method of preparing the silver halide photographic material and the packaging conditions were changed as shown in the table below. Was prepared.

 The details of each of the correction conditions in the production of the silver halide photographic light-sensitive material are as follows.

 (Adjustment of moisture content of sample)

 Moisture content 1.8%: The environment during winding was 18 and 15% RH.

 Moisture content 2.1%: The environment during winding was 18 ° (: 29% RH).

 Moisture content 3.3%: The environment during winding was 18 and 48% RH.

 Water content 3.7%: The environment during winding was 18 ° C and 61% RH.

 (Introduction of dislocation lines into silver halide emulsion)

 With respect to the silver halide emulsions g, f, and h used for preparing Sample 101, dislocation lines were introduced into the silver halide grains during grain growth according to the method described in Example 1 of JP-A-6-161006. .

 The presence or absence of dislocation lines in silver halide emulsions g, f, and h incorporating dislocation lines prepared as described above was confirmed using an electron microscope, and as a result, all emulsions showed 70% of the total projected area. It was confirmed that dislocation lines existed in the silver halide grains of not less than% by weight.

 (Addition of the compound represented by the general formula (1))

Sample 107 was prepared by adding two types of polyvinylpyrrolidone (AF-1, AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 100,000 when preparing a coating solution for each photosensitive layer. After the addition of each chemically sensitized silver iodobromide emulsion, an amount of 5 mg Zm ² was added to the coating solution, and the amount of 20 mg / m ² was added for sample 108 in the same manner. did. [Preparation of photographic film products 12 and 13]

 In the production of the above photographic film products, photographic film products 12 and 13 were produced using moisture-proof bags instead of resin cans.

 (Production of photographic film products 1 and 2)

 Photographic film product 12 (sample 104) was prepared in the same manner except that a moisture-proof material having the following composition was used instead of the resin can.

Configuration of the moisture-proof materials used, the outermost layer of a stretched nylon (ONy) 1 5 micron / oriented polypropylene (0 PP) 25 micron aluminum oxide deposited poly E Ji terephthalate (A "0 ₃ P ET) of the wrapper 2 microns Z Poryechiren (PE) 20 micron Z Ethylene vinyl acetate copolymer (EVA) 40 micron laminated in this order: The moisture permeability of this material was measured by the JISZ 0208 method to be 0.6 gZm ² '24 h (40 ° C · 90% RH) The manufacturing method is as follows: A12O3PET (1011 type film manufactured by Toyo Metallizing Co., Ltd.) is used, and a urethane-based adhesive is used. After laminating by the one-shot method, and further laminating ONy on the laminated film by the same method, the EVA film of the heat sealing layer was laminated by the extrusion lamination method of PE.

 (Production of photographic film product 13)

 Photographic film product 13 was prepared in the same manner as in the preparation of photographic film product 12 (sample 104), except that the environment in which the moisture-proof bag was packaged was changed to 23 ° (55% RH).

Details of each photographic film product are shown in the table below. Photo Sample A g X — General formula Moisture content Packaging environment Packaging material Remarks Film number Dislocation line (1) Temperature Z Humidity

mg / m ² (%) (in) Z (%)

1 1 0 1 1 2.8 23/45 Resin can Comparative example

2 1 0 2 Yuichi 1.8 23/45 Resin can Comparative example

3 1 0 3 Yuichi 3. 7 23/45 Resin can Comparative example

4 1 04 Yuichi 2.8 23/2 2 Resin can Comparative example

5 1 0 5 Yes ― 2.8 23/55 Resin can Comparative example

6 1 0 5 Yes ― 2. 1 23/45 Resin can The present invention

7 1 04 Yuichi 2.8 23/45 Resin can The present invention

8 1 0 6 Yuichi 3.3 3/45 Resin can The present invention

9 1 04 Yuichi 2.8 1 6/45 Resin can The present invention

1 0 1 0 7 Yes 5.0 2.2.8 23/45 Resin can The present invention

1 1 1 08 Yes 20.0 2.8 23/45 Resin can The present invention

1 2 1 04 Yuichi 2. 8 23/45 Moisture-proof bag The present invention

1 3 1 04 Yes-2.8 23/55 Moistureproof bag Comparative example

<Each photo film

Each of the photographic film products prepared above was processed into an unprocessed sample (reference sample) and a sealed sample 4 (a sample stored for one month at the temperature of TC (compulsory deterioration sample). I went. [Creation of characteristic curve]

 After subjecting the reference sample and the forcibly deteriorated sample to white exposure through a ゥ edge, according to the developing method described in paragraphs [0220] to [0227] of JP-A-10-123652, A color development process was performed.

 Next, for each of the color-developed samples, the transmission Status sM densities of yellow, magenta and cyan were measured using a densitometer manufactured by X_rite, which is a transmission densitometer, and the D-Log for each photograph was measured. E characteristic curve was created.

 [Evaluation of Capri concentration variability (AF o g)]

 In each characteristic curve of the reference sample and the forced deterioration sample, as a representative, the difference between the minimum magenta image density of the reference sample (Capri density: Dmin 1) and the minimum magenta image density of the forced deterioration sample (Capri density: Dxn in 2) ( Dmin in 2—Dmin) was used as a measure of Capri variability (AF 0 g).

 [Evaluation of gradation variability (Δr)]

 In each characteristic curve of the reference sample and the forced deterioration sample, a straight line connects the density point of minimum density +0.10 and the density point at the exposure point of +1.5 in the exposure area from the density point, and the slope of this straight line r (tan), and the difference Δr (1-r2) between r11 of the magenta image of the reference sample and the gradient r2 of the magenta image of the forcibly degraded sample is obtained as a representative, and this is calculated as the gradation variation. It was a measure of gender.

 [Evaluation of maximum concentration variability (ADmaX)]

In each characteristic curve of accelerated aging samples and reference sample, the difference (Dm axl _Dm ax between the maximum magenta image density of the reference sample as a representative (Dm a _X 1) and the maximum magenta image density of accelerated aging samples (D ma X 2) 2) was determined, and this was used as a measure of the maximum concentration variability (ΔDmax). The results obtained as above are shown in the following table, _c Photographic film Capri density variability Gradation variability Maximum density variability

 Δ F 0 g Δ r D m a x

0.19 0.13 0.18 Comparative example

2 0.27 0.13 0.16 Comparative Example 3 0.31 0.18 0.29 Comparative Example 4 0.26 0.12 0.15 Comparative Example 5 0.32 0.18 0.36 Comparative Example 6 0 1 0.08 0.1 1 Invention 7 0.09 0.08 0.09 Invention 8 0.16 0.10 0.12 Invention 9 0.10 0.09 0.10 Invention

10 0.06 0.06 0.07 The present invention

 0.03 0.05 0.05 The present invention

1 2 0.10 0.10 0.1 1 Invention 13 0.35 0.16 0.35 Comparative example Possibility of industrial use

 As described above, with the configuration of the present invention, a photographic film product having excellent storage stability in a packaged form could be provided.

Claims

The scope of the claims 1. A silver halide color photographic light-sensitive material having at least one red light-sensitive layer, green light-sensitive layer, blue light-sensitive layer, and non-light-sensitive layer on a transparent support is accommodated in a cartridge in a roll. Later, in a photographic film product stored in a packaging container, at least one of the light-sensitive layers contains a tabular silver halide emulsion containing 70% or more of the total projected area of silver halide grains having dislocation lines. The photographic material having a water content of not less than 2.0% and not more than 3.5% at a temperature of not less than 15 ° C and not more than 25 ° C, and a relative humidity of not less than 25%; A photographic film product characterized by being housed in a sealed container in a sealed state under an atmosphere of 50% or less.  2. The tabular silver halide emulsion according to claim 1, wherein the tabular silver halide emulsion contains tabular silver halide grains having an average aspect ratio of 8 or more in 50% or more of the total projected area. A photographic film product as described.  3. The photographic film product according to claim 1, wherein the tabular silver halide emulsion has a coefficient of variation of a particle size distribution of a circle-equivalent diameter of 15% or more and 30% or less.  4. The photographic film according to claim 1, wherein the silver halide color photographic material contains a compound represented by the following general formula (1). PQo -General formula (1)

[In the formula, represents a hydrogen atom or an alkyl group. Q represents a group of nonmetal atoms necessary to form a 5- to 7-membered ring together with N and C = 0. A and B each represent a copolymerizable ethylenically unsaturated compound. x, y, and z each represent mol%, and 10 ^ x ^ 100, 0y≤90, and 0z90. The number average molecular weight is 200 to 5200,000. ]  5. The photographic film product according to claim 1, wherein the packaging container is a sealed resin container made of a polyolefin-based resin. 6. The photographic film according to claim 1, wherein the packaging container is a moisture-proof bag having a moisture permeability of 20.0 g / m ^{2 to} 24 h (40 ° C./90% RH) or less. 0 products.