JP2008250255A - Silver halide emulsion and silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion suitable for providing a cinematographic positive film excellent in pressure resistance as well as sensitivity, and to provide a silver halide color photographic sensitive material using the emulsion. <P>SOLUTION: One grain in all silver halide grains contained in the silver halide emulsion has an average silver bromide content of 0.1-5 mol%, an average silver chloride content of ≥90 mol% and an average silver iodide content of 0.01-1.0 mol%, and the silver halide grains have a core/shell structure and contain silver iodide distributed band-like in the shell. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a silver halide emulsion and a silver halide color photographic light-sensitive material using the same. More specifically, the present invention relates to a silver halide color photographic light-sensitive material comprising a silver halide emulsion in at least one layer, and having reduced sensitivity to pressure increase / decrease fogging generated during handling. It is.

  As represented by Hollywood movies, the speed of processing can be reduced from the viewpoint of the demand for simultaneous opening at movie theaters around the world and the fact that processing in large quantities in a shorter period of time can reduce the cost of the laboratory. Is required. As a result, the transport speed during development has been increased, but as a disadvantage of increasing the speed, it is likely to cause fluctuations due to pressure, which is presumed to be caused by the film hitting the transport roller or colliding with each other. It can be said that

  In addition, as part of the reduction of the time, the speed at which the photosensitive material is transported in the processing equipment is increased, and when the foreign material mixed in the transported part or the solid matter generated from the processing liquid comes into contact with the photosensitive material, The applied local deformation energy has increased. It is well known that silver halide emulsion grains have a development center due to such deformation, and give an unfavorable color to the deformed portion. In order to maintain and improve the finished quality, the demand for pressure resistance of the photosensitive material is increasing more than ever. Problems such as pressure fog and pressure desensitization largely depend on the characteristics of the silver halide emulsion. Therefore, a silver halide emulsion excellent in pressure resistance is required.

  Various techniques for obtaining an emulsion having improved pressure resistance while increasing sensitivity are provided. Among them, as a technique for improving pressure resistance using a silver halide emulsion having an iodine-containing silver halide composition, For example, there are Patent Documents 1 to 6. However, when a movie color positive film was prepared using the silver halide emulsions disclosed in these publications, none of them had sufficient pressure resistance.

In addition to the above knowledge, as a result of searching for prior art related to a patent application that uses a dimethylsiloxane copolymer as a light-sensitive material to improve scratch resistance, the following Patent Documents 7 to 10 were found. It is known that it is different from the following problem. That is, Patent Document 7 aims to improve the printing resistance of the photosensitive lithographic printing plate, Patent Document 8 only appeals for surface lubricity, and Patent Document 9 describes the antifouling property of the optical information record carrier. For the purpose of improvement, Patent Document 10 aims to improve the friction resistance and antifouling property of optical films such as polarizing plates and display devices.
JP-A-8-262601 JP-A-8-262605 JP 2004-226434 A JP-A-6-289518 JP-A-6-289532 JP 2002-72395 A JP-A-8-160604 JP-A-10-133330 JP 2005-111756 A JP 2006-18233 A

  An object of the present invention is to provide a suitable emulsion and a silver halide color photographic light-sensitive material using the emulsion in order to provide a positive film for a movie having high sensitivity and excellent pressure suitability.

  As a result of diligent research, the present inventors have found that silver iodide is contained in the shell, and the average silver iodide content in the entire silver halide grain is 0.01 mol% or more and 1.0 mol% or less to increase the sensitivity. In addition, use of a dimethylsiloxane copolymer is recommended because of the tendency for the fog to increase and decrease in pressure in silver halide color photographic materials using an emulsion containing silver iodide in the shell. Has found that the above-mentioned problems can be solved.

That is, the said subject is solved by the means shown below.
[1] The average silver bromide content in one grain in all silver halide grains contained in the silver halide emulsion is 0.1 mol% or more and 5 mol% or less, and the average silver chloride content is 90 mol%. Silver iodide in which the average silver iodide content is 0.01 mol% or more and 1.0 mol% or less, and the silver halide grains have a core / shell structure and are distributed in a band shape A silver halide emulsion comprising:

  [2] The silver halide emulsion as described in [1], wherein the silver halide grains are a normal crystal cube or a tetradecahedral having a (100) plane on the outer surface.

[3] The support has at least one silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a cyan dye-forming coupler. A silver halide color photographic light-sensitive material for cinema, wherein the silver halide emulsion according to [1] or [2] is contained in at least one layer of the silver halide emulsion layer, and a dimethylsiloxane copolymer in at least one layer A silver halide color photographic light-sensitive material for movies, comprising 5 mg / m ² or more and 500 mg / m ² or less.

  According to the present invention, it is possible to provide a silver halide color photographic material suitable for color positive printing with high sensitivity, improved color turbidity and good pressure scratch fogging performance.

The silver halide color photographic light-sensitive material according to the present invention will be described in detail below.
First, the composition of the halogenated particles used in the present invention will be described.

  In the silver halide color photographic light-sensitive material of the present invention, the average silver bromide content in one grain in all silver halide grains contained in the silver halide emulsion is 0.1 mol% or more and 5 mol% or less. At least one silver halide emulsion having an average silver chloride content of 90 mol% or more is contained. Silver bromide may be uniformly distributed in the grains or may be localized in a part. In the case of having a localized portion, a structure in which the localized portion does not exist inside the grain is preferable, and the grain central portion (core portion) does not contain silver bromide, and silver bromide only at the outer peripheral portion (shell portion). The structure containing is preferable. It is preferable to provide a relaxation layer so as not to produce a Br content gap between the particle central portion (core portion) and the outer peripheral portion (shell portion).

  In the silver halide grains of the present invention, the average silver iodide content in one grain is 0.01 mol% or more and 1.0 mol% or less, and 0.02 mol% or more and 0.1 mol% or less. It is preferable that the silver iodide is distributed in a band shape. That is, the grain central portion (core portion) does not contain silver iodide and has a silver iodide-containing layer on the outer side (shell portion). In the iodine-containing layer, the iodine content is preferably 0.5 mol% or more and 10 mol% or less, and more preferably 1 mol% or more and 5 mol% or less.

  The silver halide grains of the present invention are normal crystal cubes or tetrahedrons having a (100) plane on the outer surface. The normal crystal may have rounded corners or rounded corners, but it is preferable that the normal crystals are rounded and the (100) plane and (111) plane are properly formed.

  Next, the photographic layers of the silver halide color photographic light-sensitive material for movie projection of the present invention will be described.

  The silver halide color photographic light-sensitive material of the present invention is a silver halide color photographic light-sensitive material for movies having a transmission type support, and a silver halide emulsion layer containing a yellow dye-forming coupler and a magenta dye are formed on the support. It has at least one each of a coupler-containing silver halide emulsion layer and a cyan dye-forming coupler-containing silver halide emulsion layer. The silver halide color photographic light-sensitive material of the present invention can be applied to general-purpose and movie color photographic light-sensitive materials such as color positive films and movie positive films, and particularly preferably to movie color positive light-sensitive materials.

  In the present invention, the number and order of the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer are not particularly limited. Each of the yellow, cyan and magenta color-sensitive photosensitive silver halide emulsion layers is composed of a plurality of silver halide emulsion layers having the same color sensitivity and different sensitivities, even if the photosensitive silver halide emulsion layer is composed of one photosensitive silver halide emulsion layer. It may be.

  There is no restriction between the color developability and color sensitivity of each color-sensitive photosensitive silver halide emulsion layer. For example, a color developable light-sensitive silver halide emulsion layer has color sensitivity in the infrared region. It doesn't matter.

  Examples of typical layer order include a non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye and / or black colloidal silver in order from the support, a yellow color-forming photosensitive silver halide emulsion layer, a non-photosensitive layer. Hydrophilic colloid layer (color mixing prevention layer), cyan color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (color mixing preventing layer), magenta color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic Colloidal layer (protective layer). However, depending on the purpose, the order of installation may be changed, or the number of photosensitive silver halide emulsion layers or non-photosensitive hydrophilic colloid layers may be increased or decreased.

The iron (Fe) in the silver halide color photographic light-sensitive material of the present invention is brought mainly by gelatin, intentionally doped emulsion grains, dyes and the like. The Fe content in the light-sensitive material of the present invention is required to be 2 × 10 ⁻⁵ mol / m ² or less (preferably 1 × 10 ⁻⁸ to 2 × 10 ⁻⁵ mol / m ² ). ^Yes, preferably 8 × 10 ⁻⁶ mol / m ² or less (preferably 1 × 10 ⁻⁸ to 8 × 10 ⁻⁶ mol / m ² ), preferably 3 × 10 ⁻⁶ mol / m ² or less (preferably 1 × 10 ^{−8 to} 3 × 10 ⁻⁶ mol / m ² ) is most preferable.

  In the present invention, gelatin is preferably used as the hydrophilic colloid. If necessary, other hydrophilic colloids can be used in place of gelatin at any ratio. Examples of these include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin or casein, cellulose derivatives (eg, hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate), saccharides such as sodium alginate and starch derivatives. And a wide range of synthetic polymers such as polyvinyl alcohol, partial acetal of polyvinyl alcohol, poly (N-vinylpyrrolidone), polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole.

  Examples of the silver halide grains include silver chloride, silver bromide, (iodo) silver chlorobromide, and silver iodobromide. In particular, in the present invention, silver chloride, silver chlorobromide, silver chloroiodide and silver chloroiodobromide having a silver chloride content of 95 mol% or more can be preferably used in order to speed up the development processing time. The silver halide grains in this emulsion are those having regular crystals such as cubes, octahedrons and tetradecahedrons, those having irregular crystal systems such as spheres and plates, twin planes, etc. Those having the above crystal defects or a composite system thereof may be used. Further, it is preferable to use tabular grains whose main plane is the (111) plane or the (100) plane in terms of speeding up color development and reducing processing color mixing. Regarding tabular high silver chloride emulsion grains having a principal plane of (111) plane or (100) plane, JP-A-6-138619, U.S. Pat. Nos. 4,399,215, 5,061,617, 5,320,938, 5,264,337, 5,292,632, 5,314,798, 5,413,904, International Publication WO94 / 22051 It can be prepared by the method disclosed in each gazette or specification of the issue.

  As the silver halide emulsion that can be used together in the present invention, a silver halide emulsion having an arbitrary halogen composition may be used. From the viewpoint of rapid processability, a salt (iodinated) salt having a silver chloride content of 95 mol% or more. Silver and silver (iodo) bromide are preferred.

  The sphere equivalent diameter of the silver halide grains constituting the silver halide emulsion used in the present invention is not particularly limited, but is preferably 1.0 μm or less, particularly preferably 0.05 μm or more and 0.7 μm or less. preferable. The emulsion used in the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation coefficient of the sphere equivalent diameter of all particles used in the present invention is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter.

  The silver halide emulsion used in the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding chemical sensitization, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, right lower column to page 22, upper right column are preferably used. The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced. For gold sensitization, a compound such as chloroauric acid or a salt thereof, gold thiocyanate or gold thiosulfate can be used. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. is there. In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using other than gold compounds. Is more preferable.

  Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, “I. Emulsion preparation and types”, and 18716 (November 1979), page 648, ibid. 307105 (November 1989), 863-865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Monter (P. Glafkides, Chemie et Physiograph Photograph, Paul Montel, 1967), "Photoemulsion Chemistry". Published by Focal Press (GF Duffin, Photographic Chemistry Chemistry, Focal Press, 1966), "Production and Coating of Photoemulsions" by Zelikman et al., Published by Focal Press (V. L. Zelikman, et al.,). (Making and Coating Photographic Emulsion, Focal Press, 1964) and the like. .

  Monodispersed emulsions described in US Pat. Nos. 3,574,628, 3,655,394, and British Patent 1,413,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); U.S. Pat. No. 4,434,226, 4 No. 4,414,310, No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157.

  The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. Also, a mixture of various crystal grains may be used.

  The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. . Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

  As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. The additive used in such a process is RDNo. 17643, ibid. 18716 and the same No. 307105, and the corresponding sections are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of a photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The coating amount of silver in film for a silver halide color photographic light-sensitive material of the present invention is preferably 6.0 g / m ² or less, more preferably 4.5 g / m ² or less, 2.0 g / m ² or less and most preferably . The applied silver amount is preferably 0.01 g / m ² or more, more preferably 0.02 g / m ² or more, and still more preferably 0.5 g / m ² or more.

In any one of the photographic constituent layers composed of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer (intermediate layer, protective layer, etc.) provided on the support, preferably a silver halide emulsion layer The 1-aryl-5-mercaptotetrazole compound is preferably added in an amount of 1.0 × 10 ^{−5 to} 5.0 × 10 ⁻² mol, and more preferably 1.0 × 10 ⁻⁴ to 1 per mol of silver halide. It is preferable to add 0.0 × 10 ⁻² mol. By adding in this range, the stain on the processed color photographic surface after the continuous processing can be further reduced.

As such a 1-aryl-5-mercaptotetrazole compound, an aryl group at the 1-position is preferably an unsubstituted or substituted phenyl group, and preferred specific examples of this substituent include acylamino groups (for example, acetylamino, -NHCOC ₅ H ₁₁ (n) etc.), ureido group (eg methylureido etc.), alkoxy group (eg methoxy etc.), carboxylic acid group, amino group, sulfamoyl group etc. A plurality (2 to 3 etc.) may be bonded. Further, the position of the substituent is preferably the meta or para position. Specific examples thereof include 1- (m-methylureidophenyl) -5-mercaptotetrazole and 1- (m-acetylaminophenyl) -5-mercaptotetrazole.

  The photographic additive that can be used or used in the present invention is described in the following Research Disclosure Journal (RD), and the following description is given.

  Various dye-forming couplers can be used in the silver halide color photographic light-sensitive material of the present invention, and the following dye-forming couplers are particularly preferred.

Yellow coupler: coupler represented by general formulas (I) and (II) of European Patent EP502,424A; coupler represented by general formulas (1) and (2) of European Patent EP513,496A (Especially Y-28 on page 18); couplers represented by general formula (I) of claim 1 of JP-A-5-307248; 45-1 of column 1 of US Pat. No. 5,066,576 Coupler represented by general formula (I) on line 55; coupler represented by general formula (I) in paragraph 0008 of JP-A-4-274425; claim 40 on page 40 of EP 498,381A1 (Especially D-35 on page 18); couplers represented by general formula (Y) on page 4 of European Patent EP447,969A1 (especially Y-1 (page 17), Y-54 ( 41)); United States The couplers represented by the formulas (II) to (IV) in columns 7 to 58 of column 7 of the specification No. 4,476,219 (particularly II-17, 19 (column 17), II-24 (column 19) )).

Magenta coupler: JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13)); European Patent EP 456,257 A-4-63 (page 134), A-4-73, -75 (page 139); European Patent EP 486,965, M-4, -6 (page 26), M-7 (page 27). ); M-45 in paragraph 0024 of JP-A-6-43611, M-1 in paragraph 0036 in JP-A-5-204106; M-22 in paragraph 0237 of JP-A-4-362631.

Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14 to 16) of JP-A-4-204843; C-7,10 (35 of JP-A-4-43345) Pages), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); and general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385 Coupler represented by Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.

  Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, German Patent GB 2,125570, European Patent EP 96,873B, German Patent DE 3,234,533. Those described in the document are preferred. A coupler for correcting unwanted absorption of the coloring dye is yellow represented by the general formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1. Colored Cyan Coupler (especially YC-86 on page 84), Yellow Colored Magenta Coupler ExM-7 (page 202, EX-1 (page 249), EX-7 (page 251), US Patent) described in the European Patent Specification No. 4,833,069, magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10), US 4,837,136 (2) (column 8), International Publication WO92 / A colorless masking coupler represented by the general formula [C-1] of claim 1 of No. 11575 (particularly, exemplified compounds on pages 36 to 45) is preferable.

  Examples of compounds (including dye-forming couplers) that react with oxidized developing agent to release photographically useful compound residues include the following.

Development inhibitor releasing compound: a compound represented by any one of the general formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (particularly T-101) (Page 30), T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), European Patent EP 436, The compound represented by the general formula (I) described on page 7 of the specification of 938A2 (particularly D-49 (page 51)), the compound represented by the general formula (1) of JP-A-5-307248 ( In particular, the compound represented by any one of the general formulas (I), (II) and (III) described in paragraph (0027) (23)) and pages 5 to 6 of European Patent EP440,195A2 (particularly page 29) I- (1));
Bleach accelerator releasing compounds: compounds represented by general formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (61) on page 61) and JP-A-6 Compound represented by the general formula (I) of claim 1 of JP-A-59411 (particularly, paragraph (7) of paragraph 0022); ligand releasing compound: described in claim 1 of US Pat. No. 4,555,478 A compound represented by LIG-X (particularly, a compound on the 21st to 41st lines of column 12);
Leuco dye releasing compounds; compounds 1-6 of columns 3-8 of US Pat. No. 4,749,641;
Fluorescent dye-releasing compound: a compound represented by COUP-DYE of claim 1 of US Pat. No. 4,774,181 (particularly compounds 1 to 11 in columns 7 to 10);
Development accelerator or fogging agent releasing compound: compound represented by general formula (1), (2), (3) in column 3 of U.S. Pat. No. 4,656,123 (especially (I- 22)) and ExZK-2 on page 75, lines 36-38 of EP 450,637A2; a compound which releases a group which becomes a dye only after leaving: Claim 1 of US Pat. No. 4,857,447 A compound represented by the general formula (I): (especially Y-1 to Y-19 in columns 25 to 36).

  As additives other than the dye-forming coupler, the following are preferable.

Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140) of JP-A-62-215272 ˜144);
Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363;
Oxidizing agent scavenger for developing agent: Compound (especially I- (1), (2), (6) in column 2, lines 54 to 62 of U.S. Pat. No. 4,978,606. ), (12) (columns 4-5)), U.S. Pat. No. 4,923,787, column 2, line 5-10, in particular compound 1 (column 3);
Stain inhibitor: General formulas (I) to (III) on page 4, lines 30 to 33 of EP 298321A, in particular I-47, 72, III-1, 27 (pages 24 to 48);
Antifading agent: A-6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164 (69 of EP 298321A) -118), U.S. Pat.No. 5,122,444, columns 25-38, II-1 to III-23, especially III-10, and EP 471347A, pages 8-12, I-1. ~ III-4, in particular II-2, U.S. Pat. No. 5,139,931, columns 32-40, A-1 to 48, in particular A-39,42;
Materials that reduce the amount of color-enhancing agent or color mixing inhibitor used: I-1 to II-15, especially I-46, pages 5 to 24 of EP 4131324A;
Formalin scavenger: European patent EP 477932A, pages 24 to 29, SCV-1 to 28, in particular SCV-8;
Hardener: H-1,4,6,8,14 on page 17 of JP-A-1-214845, general formula (VII) to columns 13-23 of U.S. Pat. No. 4,618,573 Compound (H-1 to 54) represented by (XII), Compound (H-1 to 76) represented by formula (6) at the lower right of page 8 of JP-A-2-214852, particularly H-14 A compound according to claim 1 of US Pat. No. 3,325,287;
Development inhibitor precursor: compounds described in claim 1 of P-24, 37, 39 (pages 6-7) of JP-A No. 62-168139, US Pat. No. 5,019,492, particularly column 7 28-29;
Preservatives, antifungal agents: U.S. Pat. No. 4,923,790, columns 3-15, I-1 to III-43, in particular II-1,9,10,18, III-25;
Stabilizer, antifoggant: US Pat. No. 4,923,793, columns 6-16, I-1 to (14), in particular I-1,60, (2), (13), US Pat. Compounds 1 to 65, in particular 36, in columns 25 to 32 of 4,952,483;
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324;
Dye: a-1 to b-20 on pages 15 to 18 of JP-A-3-156450, especially a-1, 12, 18, 27, 35, 36, b-5, pages V to 27 to 29 -23, in particular V-1, F-I-1 to F-II-43, in particular F-I-11, F-II-8, European patent EP 457153A, on pages 33 to 55 of EP 445627A. Pp. 17-28, III-1 to 36, especially III-1,3, European Patent EP 319999A, pages 6 to 11, Compounds 1 to 22, especially Compound 1, European Patent EP 519306A Compounds D-1 to 87 represented by (1) to (3) (pages 3 to 28), Compounds 1 to 22 represented by general formula (I) in U.S. Pat. No. 4,268,622 Columns 3-10), U.S. Pat. No. 4,923,788. A compound represented by the general formula (I) (1) ~ (31) (columns 2-9);
UV absorbers: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by general formula (1) in JP-A No. 46-3335, and general formulas of European Patent EP520938A Compounds (3) to (66) (pages 10 to 44) represented by (I) and compounds HBT-1 to HBT-10 (page 14) represented by general formula (III), European Patent EP521823 Compounds (1) to (31) represented by general formula (1): (columns 2 to 9).

  In the present invention, non-bleachable colored materials are preferably used in combination. The non-bleachable colored material does not come out of bath or lose color during development processing, and the light absorption characteristics in the film before and after the processing are practically unchanged. There is no restriction | limiting in particular about the kind, Various dyes and pigments containing a well-known substance can be used.

  Known dyes include, for example, oxonol dyes, azomethine dyes, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, arylidene dyes, styryl dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, azine dyes, oxazines And dyes, thiazine dyes, perinone dyes, merocyanine dyes, cyanine dyes, indoaniline dyes, phthalocyanine dyes, indigo dyes, and thioindigo dyes.

  As for known pigments, for example, azo pigments (insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments), phthalocyanine pigments, dyed lake pigments (acidic dye lakes, basic dye lakes), condensation Organics such as polycyclic pigments (quinacridone pigments, thioindigo pigments, perylene pigments, anthraquinone pigments, perinone pigments, dioxazine pigments, isoindolinone pigments, diketopyrrolopyrrole pigments) and others (nitroso pigments, alizarin lake pigments, alkali blue) Mention may be made of pigments.

  For specific compounds, please refer to “New Edition Dye Handbook” (Organic Synthetic Chemistry Association; Maruzen, 1970), “Color Index” (The Society of Dyers and Colorists), “Color Material Engineering Handbook” (Color Material Association Edition; Asakura Shoten) 1989), “Revised New Handbook of Pigments” and the like. As specific examples of preferred dyes and pigments, D-1 to D-35 and P-1 to P-30 described in paragraph No. 0191 to paragraph No. 0250 of JP-A No. 11-95371 can be preferably exemplified. In addition, the method for adding these to the light-sensitive material is also described in detail in paragraph Nos. 0206 to 0215 of the patent, and these described parts are incorporated as part of the specification of the present application.

In the present invention, among the above, preferably better dye than the pigment, although the amount used 1 to 100 mg / m ² is generally preferably 5 to 100 mg / m ^2, more preferably 10 to 50 mg / m ² .

The silver halide color photographic light-sensitive material of the present invention preferably contains a compound represented by the following general formula (FS) as a surfactant.

  In general formula (FS), A and B each independently represent a fluorine atom or a hydrogen atom. a and b each independently represent an integer of 1 to 6; c and d each independently represents an integer of 4 to 8. x represents 0 or 1; M represents a cation.

  A and B each independently represent a fluorine atom or a hydrogen atom, and A and B may be the same or different. A and B are each preferably a fluorine atom or a hydrogen atom, and more preferably both A and B are a fluorine atom. a and b each independently represent an integer of 1 to 6; As long as a and b are integers of 1 to 6, they may be different from each other or the same. a and b are preferably integers of 1 to 6, and a = b, more preferably an integer of 2 or 3, and a = b, and more preferably a = b = 2.

  c and d each independently represents an integer of 4 to 8. As long as c and d are integers of 4 to 8, they may be different or the same. c and d are preferably integers of 4 to 6 and c = d, more preferably 4 or 6 and c = d, and further preferably c = d = 4. .

x represents 0 or 1, both of which are likewise preferred.
M represents a cation, and as the cation represented by M, for example, alkali metal ions (lithium ions, sodium ions, potassium ions, etc.), alkaline earth metal ions (barium ions, calcium ions, etc.), ammonium ions and the like are preferable. Applied. Of these, lithium ions, sodium ions, potassium ions, and ammonium ions are particularly preferable.

Among the compounds represented by the general formula (FS), a compound represented by the following general formula (FS-a) is more preferable.

  In general formula (FS-a), a, b, c, d, M, and x have the same meanings as those in general formula (FS), and preferred ranges thereof are also the same.

Among the general formula (FS), the following general formula (FS-b) is more preferable.

  In general formula (FS-b), a1 represents the integer of 2-3. c1 represents an integer of 4 to 6. M represents a cation. x represents 0 or 1; 2 is preferable as a1. c1 is preferably 4. x is preferably 0 or 1.

Although the specific example of the preferable surfactant used for this invention is illustrated below, this invention is not limited to these specific examples.

  In the present invention, when the surfactant is used in the layer of the photographic material, the aqueous coating composition containing the surfactant may be composed of only the surfactant used in the present invention and water, depending on the purpose. And may contain other components as appropriate.

  In the above aqueous coating composition, two kinds of surfactants used in the present invention may be used, or three or more kinds may be mixed and used. Moreover, you may use another surfactant with the said surfactant. Examples of the surfactant that can be used in combination include various anionic, cationic, and nonionic surfactants, and may be a polymeric surfactant. Of these, anionic or nonionic active agents are more preferred. Examples of surfactants that can be used in combination include, for example, JP-A-62-215272 (pages 649 to 706), Research Disclosure (RD) Item 17643, pages 26 to 27 (December 1978), 18716,650. Page (November 1979), 307105, pages 875-876 (November 1989), and the like.

  A representative compound that may be contained in the aqueous coating composition is a polymer compound. The polymer compound may be a polymer soluble in an aqueous medium or an aqueous dispersion of a polymer (so-called polymer latex). The soluble polymer is not particularly limited, and examples thereof include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, and the polymer latex includes various vinyl monomers (for example, acrylates). Derivatives, methacrylate derivatives, acrylamide derivatives, methacrylamide derivatives, styrene derivatives, conjugated diene derivatives, N-vinyl compounds, O-vinyl compounds, vinyl nitriles, other vinyl compounds (for example, ethylene, vinylidene chloride)) homopolymers or copolymers And a dispersion of a condensation polymer (for example, polyester, polyurethane, polycarbonate, polyamide). Detailed examples of this type of polymer compound are disclosed in, for example, JP-A-62-215272 (pages 707 to 763), Research Disclosure (RD) Item 17643, 651 (December 1978), page 18716, 650 ( 1979), 307105, 873-874 (November 1989), and the like.

  The medium in the aqueous coating composition may be water alone, or an organic solvent other than water (for example, methanol, ethanol, isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone, etc.) and water. A mixed solvent may be used. The ratio of water in the aqueous coating medium is preferably 50% by mass or more.

  The aqueous coating composition may contain various compounds depending on the layer of the photographic photosensitive material to be used, and they may be dissolved in a medium or dispersed. Examples thereof include various couplers, ultraviolet absorbers, color mixing inhibitors, antistatic agents, scavengers, antifoggants, hardeners, dyes, and antifungal agents. In order to obtain effective antistatic ability and coating uniformity when used in a photographic light-sensitive material, it is preferably used for the uppermost hydrophilic colloid layer.

  In this case, in the coating composition of the layer, in addition to the hydrophilic colloid (for example, gelatin) and the fluorosurfactant used in the present invention, other surfactants, matting agents, slip agents, colloidal silica, gelatin A plasticizer or the like can be contained.

  There is no particular restriction on the amount of the surfactant represented by the general formula (FS), (FS-a) or (FS-b), and it is included in the structure of the surfactant, its use, and the aqueous composition. The amount used can be arbitrarily changed depending on the kind and amount of the compound to be prepared, the composition of the medium, and the like. For example, when the surfactant used in the present invention is used as a coating liquid for the uppermost hydrophilic colloid (gelatin) layer of a photographic photosensitive material which is a preferred embodiment of the present invention, the concentration (% by mass) in the coating solution is 0.003 to 2.0%, and preferably 0.03 to 10% based on the gelatin solid content.

  The silver halide color light-sensitive material of the present invention contains a dimethylsiloxane copolymer. As examples of the dimethylsiloxane copolymer, those described in JP-A-1-107255 can be used.

The amount added is preferably 5 mg / m ² or more and 500 mg / m ² or less. Too much will cause inconvenience on the surface. The layer to be added is not particularly limited, but is preferably the uppermost layer.

In the silver halide color photographic light-sensitive material of the present invention, the total hydrophilic colloid layer on the side having the emulsion layer preferably has a total film thickness of 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, 16 μm or less is particularly preferable. The total film thickness is 0.1 μm or more, preferably 1 μm or more, and more preferably 5 μm or more. Further, the film swelling speed T _1/2 is preferably 60 seconds or less, and more preferably 30 seconds or less. T _1/2 is defined as the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed for 3 minutes at 35 ° C. with a color developer is defined as the saturated film thickness. To do. The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A. Green et al. (Photogr. ScI. Eng), Vol. 19, 2, pp. 124-129 can be used for measurement. T _1/2 can be prepared by adding a hardener to gelatin as a binder or changing the aging conditions after coating.

  Further, the swelling rate is preferably 180 to 280%, and more preferably 200 to 250%. Here, the swelling ratio is a scale representing an equilibrium swelling amount when the silver halide photographic light-sensitive material of the present invention is immersed in distilled water at 27 ° C. and swollen, and the swelling ratio (unit:%) = when swollen Total film thickness / total film thickness during drying × 100. The swelling ratio can be adjusted to the above range by adjusting the amount of gelatin hardener added.

  The silver halide color photographic light-sensitive material for movies of the present invention can be processed by the standard processing steps for film positive light-sensitive materials.

Standard processing (excluding drying) for conventional film positive photosensitive materials
(1) Color developing bath (2) Stop bath (3) Washing bath (4) First fixing bath (5) Washing bath (6) Bleaching acceleration bath (7) Bleaching bath (8) Washing bath (9) Sound development (Paint development)
(10) Washing with water (11) Second fixing bath (12) Washing bath (13) Stabilizing bath In the present invention, the color development time (step (1) above) is 2 minutes 30 seconds or less among the above processing steps. (The lower limit is preferably 6 seconds or more, more preferably 10 seconds or more, still more preferably 20 seconds or more, most preferably 30 seconds or more), more preferably 2 minutes or less (the lower limit is the same as 2 minutes 30 seconds) Also gives favorable results.

Hereinafter, the support will be described.
In the present invention, a transparent support is preferable, and a plastic film support is more preferable. Examples of the plastic film support include polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polycarbonate, polystyrene, and polyethylene.

  Among these, a polyethylene terephthalate film is preferable, and a biaxially stretched and heat-set polyethylene terephthalate film is particularly preferable from the viewpoint of stability and toughness.

  Although there is no restriction | limiting in particular as thickness of the said support body, 15-500 micrometers is common, especially 40-200 micrometers is preferable from points, such as a handleability and versatility, and 85-150 micrometers is the most preferable. The transmissive support preferably means a substrate that transmits 90% or more of visible light, and contains dyed silicon, alumina sol, chromium salt, zirconium salt, etc. as long as it does not substantially interfere with light transmission. It may be.

  In order to firmly adhere the photosensitive layer to the surface of the plastic film support, the following surface treatment is generally performed. The same surface treatment is generally performed on the surface on which the antistatic layer (back layer) is formed. (1) Directly after surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxygen treatment, etc. There are two methods: a method in which a photographic emulsion (photosensitive layer forming coating solution) is applied to obtain an adhesive force, and a method (2) in which a surface layer is once treated and a subbing layer is provided and a photographic emulsion layer is applied thereon. There is a law.

  Of these, the method (2) is more effective and widely used. In any of these surface treatments, a slightly polar group is formed on the surface of the support that was originally hydrophobic, a thin layer that is a negative factor for surface adhesion is removed, It seems to increase the crosslink density and increase the adhesive strength. As a result, the affinity with the polar group of the component contained in the undercoat layer solution increases and the fastness of the adhesive surface increases. It is considered that the adhesion between the undercoat layer and the support surface is improved.

  A non-photosensitive layer containing conductive metal oxide particles is preferably provided on the surface of the plastic film support on which the photosensitive layer is not provided. As the binder for the non-photosensitive layer, acrylic resin, vinyl resin, polyurethane resin and polyester resin are preferably used. This non-photosensitive layer is preferably hardened, and as the hardener, aziridines, triazines, vinyl sulfones, aldehydes, cyanoacrylates, peptides, epoxies, melamines, etc. are used. However, from the viewpoint of firmly fixing the conductive metal oxide particles, melamine compounds are particularly preferable.

The material of the conductive metal oxide particles includes ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ and V ₂ O _5, and complex oxides thereof, and these Examples of the metal oxide further include metal oxides containing different atoms.

As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ , MgO, and V ₂ O ₅ are preferable, and SnO ₂ , ZnO, In ₂ O ₃ , TiO _2, and V ₂ are further preferable. O ₅ is preferred, and SnO ₂ and V ₂ O ₅ are particularly preferred. Examples of containing a small amount of different atoms include Zn or Al, In, TiO ₂ Nb or Ta, In ₂ O ₃ Sn, and SnO ₂ Sb, Nb or halogen elements. An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. If the amount of the different element added is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or composite oxide. If it exceeds 30 mol%, the degree of blackening of the particles increases, and charging Since the prevention layer is darkened, it is not suitable for a photosensitive material. Accordingly, the material of the conductive metal oxide particles is preferably a material containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.

  The conductive metal oxide particles are usually required to have a volume ratio of 50% or less with respect to the entire non-photosensitive layer, but preferably 3 to 30%. The coating amount is preferably in accordance with the conditions described in JP-A-10-62905. When the volume ratio exceeds 50%, dirt is likely to adhere to the surface of the processed color photograph. When the volume ratio is less than 3%, the antistatic ability does not function sufficiently.

  The particle diameter of the conductive metal oxide particles is preferably as small as possible in order to reduce light scattering as much as possible, but should be determined using the ratio of the refractive index of the particles to the binder as a parameter, and Mie's theory Can be obtained using In general, the average particle size is 0.001 to 0.5 μm, preferably 0.003 to 0.2 μm. Here, the average particle size is a value including not only the primary particle size of the conductive metal oxide particles but also the particle size of the higher order structure.

  When the metal oxide fine particles are added to the coating solution for forming the antistatic layer, they may be added and dispersed as they are, but they are dispersed in a solvent such as water (including a dispersant and a binder as necessary). It is preferably added in the form of a dispersion.

  The non-photosensitive layer preferably contains a cured product of the binder and the hardener as a binder for dispersing and supporting the conductive metal oxide particles. In the present invention, from the viewpoint of maintaining a good working environment and preventing air pollution, it is preferable to use water-soluble binders and hardeners, or use them in an aqueous dispersion state such as an emulsion. Moreover, it is preferable that a binder has any group of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with a hardening agent is possible. A hydroxyl group and a carboxyl group are preferred, and a carboxyl group is particularly preferred. The content of the hydroxyl group or carboxyl group in the binder is preferably 0.0001 to 1 equivalent / 1 kg, particularly preferably 0.001 to 1 equivalent / 1 kg.

  Hereinafter, the resin preferably used as the binder will be described. As acrylic resin, acrylic acid; acrylic acid esters such as alkyl acrylate; acrylamide; acrylonitrile; methacrylic acid; methacrylic acid esters such as alkyl methacrylate; homopolymer of any monomer of methacrylamide and methacrylonitrile Or a copolymer obtained by polymerization of two or more of these monomers. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers Is preferred. For example, a homopolymer of any one of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or a copolymer obtained by polymerization of two or more of these monomers. .

  The acrylic resin is mainly composed of a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with the hardener is possible with the above composition as a main component. It is preferable that the polymer is obtained in the above manner.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / A (meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic ester copolymer). preferable.

  The vinyl resin is polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl holmaral, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate so that a crosslinking reaction with a hardener is possible. The other polymer is a polymer obtained by partially using a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group.

  Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (eg, Polyurethane derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a mixture thereof and polyisocyanate can be given. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with the hardener.

  As the polyester resin, generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid. In the polyester resin, for example, after the reaction between the polyol and the polybasic acid is completed, the hydroxyl group and carboxyl group remaining unreacted can be used as functional groups capable of crosslinking reaction with the hardener. Of course, a third component having a functional group such as a hydroxyl group may be added. Among the above polymers, acrylic resins and polyurethane resins are preferable, and acrylic resins are particularly preferable.

  The melamine compound preferably used as a hardener includes a compound containing two or more (preferably three or more) methylol groups and / or alkoxymethyl groups in the melamine molecule and a melamine resin which is a condensation polymer thereof. Examples include melamine and urea resin. Examples of the initial condensate of melamine and formalin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, and the like. (Sumitex Resin) M-3, MW, MK, and MC (manufactured by Sumitomo Chemical Co., Ltd., all trade names), but are not limited thereto.

  Examples of the condensation polymer include hexamethylol melamine resin, trimethylol melamine resin, trimethylol trimethoxymethyl melamine resin, and the like. Commercially available products include MA-1 and MA-204 (Sumitomo Bakelite Co., Ltd., both trade names), Bekkamin MA-S, Bekkamin APM, and Bekkamin J-101 (Dainippon Ink Chemical Co., Ltd.). , All of which are trade names), Euroid 344 (trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.), Oshika Resin M31 and Oshika Resin PWP-8 (product names of Oshika Promotion Co., Ltd., both trade names). However, it is not limited to these.

  As a melamine compound, it is preferable that the functional group equivalent shown by the value which divided molecular weight by the number of functional groups in 1 molecule is 50-300. Here, the functional means a methylol group and / or an alkoxymethyl group. If this value exceeds 300, the cured density is small and a high strength cannot be obtained. If the amount of the melamine compound is increased, the coating property is lowered. If the curing density is low, scratches are likely to occur. Moreover, when the grade to harden | cure is low, the force holding an electroconductive metal oxide will also fall. If the functional group equivalent is less than 50, the curing density is increased, but the transparency is impaired, and even if the amount is reduced, it does not improve. The addition amount of the aqueous melamine compound is 0.1 to 100% by mass, preferably 10 to 90% by mass with respect to the polymer.

If necessary, the antistatic layer can be used in combination with a matting agent, a charge adjusting agent, a surfactant, a slipping agent and the like. As the matting agent, an oxide such as silicon oxide, aluminum oxide, and magnesium oxide having a particle diameter of 0.001 to 10 μm, more preferably 0.2 μm to 0.5 μm, a polymer such as polymethyl methacrylate and polystyrene, A copolymer etc. are mentioned. The preferred amount of matting agent is ^{2mg / m 2 ~15mg / m 2} .

  Examples of the charge control agent include surfactants described later, polymers containing fluorine atoms, inorganic salts, and organic salts. In particular, surfactants and polymers containing fluorine atoms, salts containing tetraalkylammonium ions, and the like are preferably used.

  Examples of the surfactant include arbitrary anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Examples of the slip agent include phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds.

  The thickness of the antistatic layer is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and thus uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior. A surface layer is preferably provided on the antistatic layer. The surface layer is provided mainly for improving the slipping property and scratch resistance and for assisting the detachment preventing function of the conductive metal oxide particles of the antistatic layer.

  Examples of the material for the surface layer include (1) wax, resin and rubber-like ones or copolymers of 1-olefinic unsaturated hydrocarbons such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Products (for example, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer and propylene / 1-butene copolymer), (2) A rubbery copolymer of two or more kinds of the 1-olefin and a conjugated or non-conjugated diene (for example, an ethylene / propylene / ethylidene norbornene copolymer, an ethylene / propylene / 1,5-hexadiene copolymer, and Isobutene / isoprene copolymer), (3) a copolymer of 1-olefin and conjugated or non-conjugated diene (for example, ethylene / Tadiene copolymers and ethylene / ethylidene norbornene copolymers), (4) 1-olefins, especially copolymers of ethylene and vinyl acetate and complete or partially saponified products thereof, and (5) 1-olefins alone or copolymerized. Examples thereof include, but are not limited to, a graft polymer obtained by grafting the above conjugated or non-conjugated diene or vinyl acetate onto a polymer, and a completely or partially saponified product thereof. The above compound is described in JP-B-5-41656.

  Among these, polyolefins having a carboxyl group and / or a carboxylate group are preferable. Usually used as an aqueous solution or aqueous dispersion.

  Water-soluble methylcellulose having a methyl group substitution degree of 2.5 or less may be added to the surface layer, and the addition amount is preferably 0.1 to 40% by mass with respect to the total binder forming the surface layer. The water-soluble methylcellulose is described in JP-A-1-210947.

  The surface layer may be formed on the antistatic layer by a well-known coating method such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, or extrusion coating. It can form by apply | coating the coating liquid (aqueous dispersion or aqueous solution) containing etc.

  The thickness of the surface layer is preferably 0.01 to 1 μm, more preferably 0.01 to 0.2 μm. If the thickness is less than 0.01 μm, it is difficult to uniformly apply the coating agent, and thus uneven coating tends to occur on the product. If it exceeds 1 μm, the antistatic performance and scratch resistance may be inferior.

  The pH of the film in the silver halide color photographic light-sensitive material of the present invention is preferably 4.6 to 6.4, and more preferably 5.5 to 6.5. When the coating pH is higher than 6.5 in a long-time sample, the sensitization of the cyan image and the magenta image due to safelight irradiation is large. Conversely, when the coating pH is lower than 4.5, the photosensitive material is exposed. The yellow image density changes greatly with respect to the time change until development. Either case is a practical problem.

  The coating pH in the silver halide color photographic light-sensitive material of the present invention is the pH of all photographic layers obtained by coating the coating solution on the support and does not necessarily match the pH of the coating solution. The coating pH can be measured by the following method as described in JP-A-61-245153. That is, (1) 0.05 ml of pure water is dropped on the surface of the light-sensitive material coated with the silver halide emulsion. Next, (2) after standing for 3 minutes, the coating pH is measured with a surface pH measurement electrode (GS-165F, trade name, manufactured by Toa Denpa). The coating pH can be adjusted using an acid (for example, sulfuric acid or citric acid) or an alkali (for example, sodium hydroxide or potassium hydroxide) as necessary.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited thereto.

Example 1
[Preparation of support]
Subjecting a primer on the emulsion paint設面side, an acrylic resin layer containing a side opposite to the below of the conductive polymer (0.05g / m ²⁾ and tin oxide fine particles (0.20g / m ²⁾ of emulsion paint設面the A coated polyethylene terephthalate film support (thickness: 120 μm) was prepared.

[Preparation of silver halide emulsion]
-Preparation of blue-sensitive silver halide emulsion-
(BM-01)
(Cube, particle size 0.52μm, particle size variation coefficient 9%)
By adding a silver nitrate aqueous solution and a potassium halide aqueous solution mixed with potassium iodide, sodium chloride and potassium bromide by a control double jet method known in the art, emulsions of samples BM-01 to BM-07 shown in the following table Was prepared. During the particle formation, the temperature of the reaction vessel was maintained at 52 ° C. and the pAg was maintained at 6.6. Taking as an example the preparation of sample BM-03 in the table below, a silver chloride layer using an aqueous potassium halide solution consisting of potassium chloride only until 80% of the total silver nitrate used from the start of silver halide grain formation is used. The silver chlorobromide layer is formed using an aqueous potassium halide solution in which potassium bromide and potassium chloride are mixed at a molar ratio of 2.5: 97.5 until 90% of the total silver nitrate is used. And then using an aqueous potassium halide solution in which potassium iodide, potassium bromide, and potassium chloride are mixed at a molar ratio of 0.5: 2.5: 97 until 100% of the total silver nitrate is used. A silver iodobromide layer was formed. An iridium compound was added to the silver chlorobromide layer. To this emulsion, sensitizing dyes (A ′) to (C ′) represented by the structural formula described later were added as follows. Samples BM-01, 02, 04-07 were prepared according to the example.

Blue sensitizing dye (A ′); 4.9 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 4.3 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′); 2 0.7 × 10 ⁻⁵ mol / mol silver Further, gold sulfur was sensitized optimally using chloroauric acid and triethylthiourea.

-Preparation of red-sensitive silver halide emulsion-
Large size emulsion (RO-01)
(Cube, particle size 0.22 μm, particle size variation coefficient 11%)
It was prepared by adding a silver nitrate aqueous solution and a potassium halide aqueous solution mixed with potassium iodide, sodium chloride and potassium bromide by a control double jet method known in the art. During particle formation, the temperature of the reaction vessel was kept at 60 ° C. and the pAg was kept at 6.6. A silver chloride layer is formed using an aqueous potassium halide solution consisting only of potassium chloride from the start of formation of silver halide grains until 50% of the total silver nitrate used is used, and then 75% of the total silver nitrate is used. Until a silver chlorobromide layer is formed using an aqueous potassium halide solution in which potassium bromide and potassium chloride are mixed at a molar ratio of 6:94, and then 100% of the total silver nitrate is used. A silver chlorobromide layer was formed using an aqueous potassium halide solution in which potassium bromide and potassium chloride were mixed at a molar ratio of 13:87. An iridium compound was added to the silver chloride layer. The iridium content was adjusted to 4 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (D ′) to (F ′) represented by the structural formula described later were added as follows and spectrally sensitized.

Red-sensitive sensitizing dye (D ′): 4.4 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 0.4 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.2 × 10 ⁻⁵ mol / mol silver Further, gold chloride is sensitized optimally using chloroauric acid and triethylthiourea, and then Cpd-71 represented by the structural formula described below is halogenated. 9.4 × 10 ⁻⁴ mol was added per 1 mol of silver.

Medium size emulsion (RM-01)
(Cube, particle size 0.17 μm, particle size variation coefficient 12%)
The sensitizing dyes (D ′) to (F ′) represented by the structural formulas described later were used as described below in the same manner as RO-01 except that the particle formation temperature was changed.

Red-sensitive sensitizing dye (D ′): 7.0 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 1.0 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.4 × 10 ⁻⁵ mol / mol silver small size emulsion (RU-01)
(Cube, particle size 0.12 μm, particle size variation coefficient 13%)
The sensitizing dyes (D ′) to (F ′) represented by the structural formulas described later were used as described below in the same manner as RO-01 except that the particle formation temperature was changed.

Red-sensitive sensitizing dye (D ′): 8.9 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 1.2 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (F ′ ): 0.5 × 10 ⁻⁵ mol / mol silver -Preparation of green-sensitive silver halide emulsion-
Large emulsion (GO-01)
(Cube, particle size 0.19 μm, particle size variation coefficient 11%)
It was prepared by adding a silver nitrate aqueous solution and a potassium halide aqueous solution in which sodium chloride and potassium bromide were mixed at a molar ratio of 1:99 by a control double jet method known in the art. K ₂ [IrCl ₆ ] was prepared to be 2 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (G ′) to (J ′) represented by the structural formula described later were added as follows and spectrally sensitized.

Green sensitive sensitizing dye (G ′): 2.6 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 0.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.2 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver Further, using chloroauric acid and triethylthiourea, Gold sulfur sensitized.

Medium size emulsion (GM-01)
(Cube, particle size 0.14 μm, particle size variation coefficient 13%)
GM-01 was prepared in the same manner as GO-01 except that the size was adjusted. Sensitizing dyes (G ′) to (J ′) represented by the structural formula described below were used as follows.

Green sensitive sensitizing dye (G ′): 3.8 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 1.3 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.4 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver Further, using chloroauric acid and triethylthiourea, Gold sulfur sensitized.

Small emulsion (GU-01)
(Cube, particle size 0.094 μm, particle size variation coefficient 19%)
GU-01 was prepared in the same manner as GO-01 except that the size was adjusted. Sensitizing dyes (G ′) to (J ′) represented by the structural formula described below were used as follows.

Green sensitive sensitizing dye (G ′): 5.1 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (H ′): 1.7 × 10 ⁻⁴ mol / mol silver Green sensitive sensitizing dye (I ′ ): 1.9 × 10 ⁻⁴ mol / mole silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mole silver Further, optimally using chloroauric acid and triethylthiourea Gold sulfur sensitized.

The halogen composition of this emulsion is Br / Cl = 1/99 (molar ratio).

[Preparation of dye solid fine particle dispersion]
The methanol wet cake of the compound (HD-1) was weighed so that the net amount of the compound was 240 g, 48 g of the following compound (Pm-1) was weighed as a dispersion aid, and water was added to make 4000 g. 'Flow-through sand grinder mill (UVM-2)' (manufactured by IMEX K.K.) is filled with 1.7 liters of zirconia beads (0.5 mm diameter), the discharge rate is 0.5 liter / min, and the peripheral speed is 10 m / s. For 2 hours. Thereafter, the dispersion was diluted so that the compound concentration was 3% by mass, and a compound (Pm-1) represented by the following structural formula was added by 3% by mass with respect to the dye (referred to as Dispersion A). The average particle size of this dispersion was 0.45 μm.

Further, a dispersion containing 5% by mass of the compound (HD-2) (referred to as Dispersion B) was obtained in the same manner.

[Preparation of Sample 101]
Each layer having the composition as shown below was coated on the support in a multilayer manner to prepare Sample 101 which was a multilayer color photographic light-sensitive material.
-Layer structure-
The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion coating amount represents a silver equivalent coating amount. Further, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener.

[Layer structure of sample 101]
Support / first polyethylene terephthalate film (halation-preventing layer (non-photosensitive hydrophilic colloid layer))
Gelatin 1.03
Dispersion A (as dye coating amount) 0.10
Dispersion B (as dye coating amount) 0.03.

Second layer (blue sensitive silver halide emulsion layer)
Silver chlorobromide emulsion BM-01 0.57
Gelatin 2.71
Yellow coupler (ExY ') 1.19
(Cpd-41) 0.0006
(Cpd-42) 0.01
(Cpd-43) 0.05
(Cpd-44) 0.003
(Cpd-45) 0.012
(Cpd-46) 0.001
(Cpd-54) 0.08
(Cpd-65) 0.02
Solvent (Solv-21) 0.26.

Third layer (color mixing prevention layer)
Gelatin 0.59
(Cpd-49) 0.02
(Cpd-43) 0.05
(Cpd-53) 0.005
(Cpd-61) 0.02
(Cpd-62) 0.03
Solvent (Solv-21) 0.06
Solvent (Solv-23) 0.04
Solvent (Solv-24) 0.002.

Fourth layer (red-sensitive silver halide emulsion layer)
2: 2: 6 mixture of silver chlorobromide emulsion RO-01, emulsion RM-01 and emulsion RU-01 (silver molar ratio) 0.40
Gelatin 2.79
Cyan coupler (ExC ') 0.80
(Cpd-47) 0.06
(Cpd-48) 0.06
(Cpd-50) 0.03
(Cpd-53) 0.03
(Cpd-57) 0.05
(Cpd-58) 0.01
(Cpd-60) 0.02
Solvent (Solv-21) 0.53
Solvent (Solv-22) 0.28
Solvent (Solv-23) 0.04.

5th layer (color mixing prevention layer)
Gelatin 0.56
(Cpd-49) 0.02
(Cpd-43) 0.05
(Cpd-53) 0.005
(Cpd-62) 0.03
(Cpd-64) 0.002
Solvent (Solv-21) 0.06
Solvent (Solv-23) 0.04
Solvent (Solv-24) 0.002.

Sixth layer (green sensitive silver halide emulsion layer)
Silver chlorobromide emulsion GO-01, emulsion GM-01,
Emulsion GU-01 mixing ratio 1: 2: 7 mixture (silver molar ratio)
0.54
Gelatin 1.66
Magenta coupler (ExM ') 0.73
(Cpd-49) 0.013
(Cpd-51) 0.001
Solvent (Solv-21) 0.15
7th layer (protective layer)
Gelatin 0.97
Acrylic resin (average particle size 2 μm) 0.002
(Cpd-55) 0.005
(Cpd-56) 0.08
(Cpd-59) 0.03
The compounds used here are shown below.

<Preparation of Samples 102 to 107>
Samples 102 to 107 were prepared in the same manner as in the preparation of sample 101 except that the emulsion BM-01 in the second layer was changed to BM-02 to BM-07, respectively.

<Preparation of Samples 108 to 114>
Further, in the photosensitive material BM101 to 107, the seventh layer (protective layer) further contains 100 mg / m ^{2 of the following} dimethylsiloxane copolymer.

Dimethylsiloxane copolymer: XF-96 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.

<Preparation of Samples 115 to 121>
Samples 115 to 121 of the photosensitive material in which the amount of the uppermost silicone oil was increased to 1000 mg / m ² were prepared.

(Evaluation of sensitivity)
Using a sensitometer (FW type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K), gradation exposure for sensitometry at 60,000 lux for 1/1000 second through a gray filter that produces maximum density And processed according to the ECP-2 process published by Eastman Kodak Company. The concentration of the treated sample was measured. For sensitivity display, the sensitivity is defined as the relative value of the logarithm of the reciprocal of the exposure amount necessary for the optical density to be increased by Dmin + 1.5. Higher values mean that the sensitivity is higher and the light is less sensitive. Each sample was evaluated for the temperature and humidity environment during exposure as follows.

(Evaluation of pressure)
A needle was set up perpendicularly to the emulsion surface of the sample before exposure, and with the load applied from above the needle, the needle was scanned horizontally to apply local pressure to the sample. A round needle having a tip shape of 0.1 mmφ was used as the needle. During one scan, the weight was kept constant and the scan was performed multiple times with the weight being varied in the range of 1-10 g. The sample was developed through the processing A without applying light, and the color fogging of the emulsion layer portion was observed to evaluate the pressure fog sensory. Each sample was relatively evaluated and divided into three stages and represented by ○ (good), Δ (medium), and × (bad). ○ and Δ are practical levels.

  As described above, when the emulsion of BM-104 to 107 is used, the generation of scratches (including pressure-sensitive increase / decrease sensation streaks) worsens.

  In combination with silicone oil, which has been used for the purpose of improving the slipping of cinematographic materials and reducing the generation of scraps and running noise, the above-mentioned improvement of sliding is not only an unexpected effect, but also scratches. Occurrence (including pressure-sensitive increase / decrease streaks) was also improved.

In the system in which 1000 mg / m ^{2 of} silicone oil was added to the seventh layer, an adhesion failure occurred and evaluation was impossible.

Claims (3)

  The average silver bromide content in one grain in all silver halide grains contained in the silver halide emulsion is 0.1 mol% or more and 5 mol% or less, and the average silver chloride content is 90 mol% or more. The silver iodide grains having an average silver iodide content of 0.01 mol% or more and 1.0 mol% or less and having a core / shell structure and distributed in a band shape A silver halide emulsion characterized by comprising:   2. The silver halide emulsion according to claim 1, wherein the silver halide grains are a normal crystal cube or a tetrahedron having a (100) plane on the outer surface. Movie halogen having at least one silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a cyan dye-forming coupler on a support A silver halide color photographic light-sensitive material, wherein the silver halide emulsion according to claim 1 or 2 is contained in at least one of the silver halide emulsion layers, and dimethylsiloxane copolymer is contained in at least one layer at 5 mg / m ^2. A silver halide color photographic light-sensitive material for cinema, characterized by containing not less than 500 mg / m ² or less.