JP2006098689A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive silver halide color photographic material for a movie which makes it possible to impart a technique for increasing the developing speed of a yellow developing image layer of an image portion. <P>SOLUTION: The silver halide color photographic sensitive material includes on a transparent support a yellow developing photosensitive silver halide emulsion layer, a cyan developing photosensitive silver halide emulsion layer and a magenta developing photosensitive silver halide emulsion layer, wherein the silver halide color photographic sensitive material contains a compound capable of releasing a diffusion resistant bleaching inhibitor by reaction with the oxidized body of a developing agent, photosensitive silver halide grains contained in the yellow developing photosensitive silver halide emulsion layer have an average grain size of ≤0.4 μm and a silver chloride content of ≥95 mol% with respect to the a total silver amount, and the photosensitive silver halide grains include photosensitive silver halide grains in which iodide ions have a concentration maximum in grain surfaces and the iodide ion concentration lowers inward. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a silver halide color photographic light-sensitive material for a movie capable of realizing a large rapid processing by a simplified and shortened processing step.

  As a means for recording sound, the music industry changed from recording to CD, and in the 1980s, it changed rapidly from analog to digital. Furthermore, a DVD having a large capacity as a recording medium including an image has penetrated the market. Magnetic materials represented by cassette tapes have also been improved in storage capacity by adopting a perpendicular magnetic recording system and developing a recording medium such as a magneto-optical recording system, and can be accessed randomly. In the movie industry, an analog soundtrack has been used as an audio recording method since the film-type talkie was invented in the 1920s by the US Dofaley and others. For audio recording in the film industry, a noise reduction method developed by Dolby Corporation was announced, and high-quality analog audio is now provided. Furthermore, from the late 1980s to the early 1990s, several formats for digitizing movie audio, such as the Dolby Stereo SR-D system by Dolby Laboratories and the SDDS system by SONY, were announced. More movies are being screened with digital audio. However, it is still in a format that can be used together with analog sound even in the event that the digital recording information is accidentally accidentally made unplayable, and analog sound has been used for audio recording in almost all movies up to now. This is the situation.

  As a method of reading the information of this analog sound track, it is transmitted through the analog sound track portion that is area-modulated by a photoelectric tube having high sensitivity in the infrared region of 750 nm to 850 nm and recently a silicon photodiode having an absorption maximum near 900 nm. The optical modulation signal information thus detected is detected as audio information, and the optical signal is converted into an electrical signal and screened as audio information. Since the detection wavelength is in the infrared region, it is necessary for the analog soundtrack to record audio information as a silver image, and the silver image remains in the analog soundtrack even today when movie films are colored. Therefore, in the processing of movie films, a special process for obtaining a silver image by applying a silver developer only to the analog sound track part is still performed after the process of processing the image part. Such precise and time-consuming processing is a considerable burden on the laboratory.

  On the other hand, in October 1996, at the SMPTE Technical Conference / World Media Exposition, a red track was used as an exciter, and a die track method for recording audio information with a cyan coloring dye instead of silver on an analog sound track It has been announced. In this report, a sound track reading device using a red LED light source that can eliminate the need for special processing to obtain a silver image by applying a developer as described above is described. To date, red LED analog readers have been actively sold, but after converting red LEDs and sound into electrical signals for each projector that has been installed in each theater from the old days, as in the digital format. It is necessary to deal with facilities such as electric signal amplifiers, and the response to all theaters has not progressed easily. Considering theaters that are not equipped with equipment, we recommend that you change to a high magenta sound track that can use the same sound negative as the cyan dye track, and this is a pre-stage to the change to cyan dye sound. The fact is that the silver-remaining treatment is still being carried out.

  In order to realize simple processing of movie prints in the lab, there is no need to introduce equipment into the theater, and as a means that enables omission of development and development of analog soundtracks, for example, Patent Documents 1 to 13 disclose bleaching suppression. A technique is disclosed that contains an agent or a bleach inhibitor releasing coupler and allows the sound information of the sound track part to be left as a silver image, thereby omitting the development development of the sound track. These techniques are very excellent techniques for simplification of processing.

On the other hand, in addition to simplifying the processing process, the positive film for movies to be screened is further provided with a development laboratory (laboratory) for screening at each theater and shipped to the theater. Then, it is necessary to prepare a very large number of screening films in a short period of time. Therefore, in addition to the technology that simplifies the processing as described above, the exposure time of the film is further shortened, the film production per unit time is increased, and the time for preparing an enormous number of films is reduced. A technology that can be shortened is desired. In order to increase the production amount per unit time, it is necessary to increase the linear velocity of each processing step in addition to the need for the application and development of the analog sound track portion. In order to increase the processing speed, in addition to painting and developing, the development process of the positive photosensitive material for movies is rate-limiting, and improvement has been desired.
U.S. Pat. No. 3,705,208 US Pat. No. 3,705,799 U.S. Pat. No. 3,705,800 US Pat. No. 3,705,801 US Pat. No. 3,705,802 US Pat. No. 3,705,803 US Pat. No. 3,737,312 US Pat. No. 3,749,572 JP-A 49-103629 Japanese Patent Laid-Open No. 51-077334 Japanese Patent Laid-Open No. 51-151134 JP 53-1225836 A Japanese Patent Laid-Open No. 55-110242

  The present invention provides a yellow color image layer of an image portion which has been rate-limited to realize an improvement in processing speed by freeing from analog sound track information application and development in order to increase the processing performance of a photosensitive material for movies per unit time. An object of the present invention is to provide a light-sensitive silver halide color photographic material for a movie which can be provided with a technique for greatly improving the developing speed.

As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by the following means.
(1) In a silver halide color photographic material having a yellow color developing photosensitive silver halide emulsion layer, a cyan color developing photosensitive silver halide emulsion layer, and a magenta color developing photosensitive silver halide emulsion layer on a transparent support, The photosensitive silver halide grains containing a compound that reacts with an oxidant of the above to release a non-diffusible bleach inhibitor and is contained in the yellow color developing photosensitive silver halide emulsion layer have an average grain size of 0.4 μm. And the silver chloride content based on the total silver amount is 95 mol% or more, and the photosensitive silver halide grains have iodide ions having a maximum concentration on the grain surface, and iodide ions are directed toward the inside. A silver halide color photographic light-sensitive material comprising photosensitive silver halide grains having a reduced density.
(2) In a silver halide color photographic light-sensitive material having a yellow color-sensitive silver halide emulsion layer, a cyan color-sensitive silver halide emulsion layer, and a magenta color-sensitive silver halide emulsion layer on a transmissive support, the developing agent The photosensitive silver halide grains contained in the yellow-colored photosensitive silver halide emulsion layer contain a compound that reacts with an oxidant of the above to release a non-diffusible bleach inhibitor and silver chloride relative to the total silver amount. A silver halide color photographic material comprising a tabular photosensitive silver halide grain having a content of 95 mol% or more and an aspect ratio of 2 or more.
(3) The silver halide color photographic light-sensitive material according to claim 2, wherein the main plane of the tabular photosensitive silver halide grains is a {100} plane.

  In the present invention, in order to provide information without applying development to the infrared region, which is a detection sensitivity region of a photoelectric tube or a silicon photodiode, for detecting information of an analog sound track, it reacts with an oxidant of a color developing agent. And an auxiliary layer containing a compound that releases a diffusion-resistant bleach inhibitor. Further, the present invention is a step after the development step in which a bleaching inhibitor is released from the auxiliary layer in the processing step of forming an image with a normal yellow coloring dye forming layer, a magenta coloring dye forming layer, and a cyan coloring dye forming layer. The present invention relates to a compound in which a silver image remains unbleached in a bleaching step and can finally record sound as a silver image on a sound track layer. Here, “soundtrack can be formed” means that the infrared density difference between the pigment coloring portion and the white background portion is 0.7 or more as measured with a Macbeth TD206A densitometer.

  Examples of the compound that reacts with an oxidized form of a color developing agent to release a diffusion-resistant bleach inhibitor include US Pat. No. 3,705,801, US Pat. No. 3,705,799, and WO 97/2147. Couplers described in US Pat. No. 4,248,962, hydroquinones releasing diffusible bleach inhibitors, naphthoquinones, and the like can be preferably used. These have a hydrophobic group bonded to the aromatic nucleus via a thio or seleno group, and react with an oxidized form of the developing agent to bind to the aromatic nucleus via a thio or seleno group Releases sex groups. In general, couplers, hydroquinones, and naphthoquinones as described above are generally known thio-substituted development inhibitor releasing compounds, such as U.S. Pat. Couplers of the compounds described in US Pat. Nos. 3,632,345, 3,705,799, and 3,705,803, and generally known mercapto compounds such as JP-A-2002-162707. The compounds described in JP-A No. 2004-54025 and the like can be preferably used.

  A thiol compound or a selenol compound can be preferably used as a diffusion-resistant bleach inhibitor that reacts with an oxidized form of a color developing agent and is released. Particularly preferably, a thiol compound can be used. In the present invention, for example, a compound represented by the following general formula I or II can be preferably used.

A in general formula (I) and B in general formula (II) are part of a coupler that reacts with an oxidized form of a color developing agent to release a thiol compound of general formula (I) or general formula (II). And hydroquinone and naphthoquinone. And R ₁ in the general formula (I), R ₂ in the general formula (II) preferably represents a substituted or unsubstituted alkyl group, an aryl group, an aralkyl group, a phenyl group. More preferred are an alkyl group and an aryl group. The preferable number of carbon atoms for R ₁ and R ₂ is preferably large, preferably 2 to 40, and more preferably 5 to 40. Specific examples are given below, but the present invention is not limited thereto.

  In order to contain these compounds in the silver halide light-sensitive material of the present invention, a new light-sensitive emulsion layer may be provided as an auxiliary layer and introduced therein, or other silver halide emulsion layers or hydrophilic layers may be introduced. It may be introduced into the conductive colloid layer. In the latter case, it is preferable to add to the intermediate layer between the image color forming layers, for example, the yellow color image forming layer and the magenta color image forming layer.

Although there is no particular limitation on the amount of non-diffusible bleach inhibitor that is reacted to release an oxidation product of a developing agent, 1 × 10 ^-7 mol / m ² or more, 5 × 10 ^-1 mol / m ² The following is preferable, and 1 × 10 ⁻⁵ mol / m ² or more and 1 × 10 ⁻¹ mol / m ² or less are more preferable.

  The color developing agent in the present invention is, for example, a known directional primary amine color developing agent, particularly a p-phenylenediamine derivative, and examples are shown below.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl-Nn-propyl- Aniline 13) 4-Amino-N- (4-carbamoylbutyl-Nn-propyl-3-methylaniline 14) N- (4-Amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4 -Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide

  Of the above, 2) is particularly preferable.

  The present invention relates to a technique for increasing the developing speed of color development processing, which is the rate-limiting of each processing step, in the processing step of a color positive photosensitive material for movies. The rate-determining factor for color development is the development rate of the yellow color-developing layer located in the lowermost layer and having a large particle size. The halogen composition of the yellow color-developable photosensitive silver halide grains used in the present invention is characterized by containing silver halide having a high development processing speed and a high fixing rate and high silver chloride content. Specifically, the silver chloride content of all silver halide grains is 95 mol% or more, preferably 96 mol% or more, and more preferably 97 mol% or more. Silver chloride, silver chlorobromide, silver chloroiodide, Or silver chloroiodobromide is preferable. Furthermore, each color-forming layer often contains two or more types of silver halide grains with different silver halide grain sizes or light absorptivity (sensitivity) for the purpose of obtaining a desired gradation. The silver chloride content of all silver halide grains in the same color developing layer with different grain size or light absorption rate (sensitivity) need not be in the above range, but more preferably the same in the same color developing layer. It is preferable that the silver chloride content of silver halide grains having the same particle size or the same light absorption rate (sensitivity) is included in the above range.

  As the halogen composition of the photosensitive silver halide grains used in the present invention, silver chloride is preferred, but when the halogen composition is within the scope of the present invention, silver chlorobromide, silver chloroiodide, chloroiodoodor It may be silver fossil. There is no particular limitation on the use of halogen other than silver chloride, and silver halide grains having a so-called core / shell structure may be used during silver halide grain formation. During precipitation aggregation, during the dispersion step, Different halogen composition phases can also be formed on the particle surface by causing halogen conversion due to the difference in solubility product during the chemical sensitization process or after the chemical sensitization and before coating.

  The average particle size of the yellow color-forming photosensitive silver halide grains of the present invention is preferably 0.4 μm or less in order to increase the developing speed. More preferably, it is 0.38 μm or less and 0.05 μm or more. The average grain size referred to in the present invention is a value standardized by the ratio of silver used when silver halides having different grain sizes are used in a blend.

  The silver halide emulsion of the present invention preferably contains silver iodide. In particular, the yellow photosensitive silver halide emulsion preferably contains silver iodide. As a method of introducing iodide ions, a method of adding an iodide salt solution alone or a method of adding an iodide salt solution together with addition of a silver salt solution and a high chloride salt solution may be employed. . In the latter case, an iodide salt solution and a high chloride salt solution may be added separately or as a mixed solution of iodide salt and high chloride salt. The iodide salt is added in the form of a soluble salt such as an alkali iodide salt or an alkaline earth iodide salt. Alternatively, the method of introducing iodide by cleaving iodide ions from organic molecules as described in US Pat. No. 5,389,508 may be employed. Further, fine silver iodide grains can be used as another iodide ion source.

  The addition of the iodide salt solution may be concentrated in one period of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Accordingly, the addition of the iodide salt solution is preferably from outside 50% of the grain volume, more preferably from outside 70%, and most preferably from outside 80%. Further, the addition of the iodide salt solution is preferably finished inside 98% of the particle volume, and particularly preferably finished inside 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained.

  The distribution of iodide ion concentration in the depth direction in the grain can be measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. . The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. When the silver halide emulsion of the present invention contains silver iodide, the iodide ion has a maximum concentration on the grain surface and the iodide ion concentration is attenuated inward by the analysis by the etching / TOF-SIMS method. It was confirmed that

  Examples of the shape of the silver halide grains include cubes, octahedrons, tabular grains, spherical grains, rod-shaped grains, potato grains, etc., but in the present invention, cubic grains and tabular grains are preferred, Tabular grains are preferably used for the purpose of imparting high sensitivity and performance with good graininess. In the present invention, tabular grains refer to grains having an aspect ratio (diameter / thickness) greater than 1, and average aspect ratio refers to the average of the aspect ratios of individual tabular grains. The diameter refers to the diameter of a circle having an area equal to the projected area of the tabular grains, and the thickness refers to the distance between two main planes. The main plane means a surface having the largest area of tabular grains. The projected area of the tabular grains and the average aspect ratio when tabular silver halide grains are used are preferably 2 or more, more preferably 2 or more and 100 or less, and more preferably 3 or more and 50 or less. Further, grains having rounded corners of silver halide grains can be preferably used. The surface index (Miller index) of the surface of the photosensitive silver halide grain is not particularly limited, but it is preferable that the ratio of the {100} plane having high spectral sensitizing efficiency when the spectral sensitizing dye is adsorbed is high. . The ratio is preferably 50% or more, more preferably 65% or more, and still more preferably 80% or more. The ratio of the Miller index is determined by T. using the adsorption dependency of {111} and {100} planes in the adsorption of a sensitizing dye. Tani; Imaging Sci. 29, 165 (1985).

  The tabular grains that can be used in the present invention are preferably tabular grains having {100} as the main plane, which has high spectral sensitization efficiency. The shape of a tabular grain having a {100} plane as a main plane is a right-angled parallelogram shape, or a 3-5 pentagon shape lacking one corner of the right-angled parallelogram (the missing shape is its angle As a vertex and a right-angled triangle portion formed by sides forming the corners thereof), or a 4-8 octagonal shape having two or more and four or less missing portions. If a right-angled parallelogram shape that compensates for the missing portion is a supplementary quadrilateral, the ratio of adjacent sides (long side length / short side length) of the right-angled parallelogram and the supplemental quadrilateral is 1-6. , Preferably 1-4, more preferably 1-2.

  As a method for forming tabular silver halide emulsion grains having {100} main planes, an aqueous silver salt solution and an aqueous halide salt solution are added and mixed in a dispersion medium such as an aqueous gelatin solution while stirring. At this time, for example, in JP-A-6-301129, 6-347929, 9-34045, and 9-96881, silver iodide or iodide ion, or silver bromide or bromide ion is present. And a method of introducing a crystal defect that imparts anisotropic growth properties such as screw dislocations by causing strain in the nucleus due to the difference in the size of the crystal lattice from silver chloride. When the screw dislocation is introduced, the formation of two-dimensional nuclei on the surface is no longer promoted under low supersaturation conditions, so that crystallization proceeds on this surface, and by introducing the screw dislocation, tabular grains are formed. It is formed. Here, the low supersaturation condition is preferably 35% or less, more preferably 2 to 20% at the time of critical addition. Although the crystal defects are not determined to be screw dislocations, it is considered that there is a high possibility of screw dislocations because the direction in which the dislocations are introduced or because anisotropic growth is imparted to the grains. In order to make the tabular grains thinner, it is disclosed in JP-A-8-122954 and JP-A-9-189977 that the introduced dislocation retention is preferable.

  JP-A-6-347928 uses imidazoles and 3,5-diaminotriazoles, and JP-A-8-339044 uses polyvinyl alcohols to add {100} surface formation accelerators. A method of forming tabular grains having a {100} major plane is disclosed. Furthermore, U.S. Pat. Nos. 5,320,935, 5,264337, 5,292,632, 5,314,798, 5,413,904, WO94 / 22051, etc. It can be prepared by the method disclosed in the above. However, the present invention is not limited to these.

  The particles of the present invention may have a so-called core / shell structure consisting of a core part and a shell part surrounding the core part. When having a core / shell structure, 90 mol% or more of the core portion is preferably silver chloride. The core portion may further comprise two or more portions having different halogen compositions. The shell portion is preferably 50% or less, particularly preferably 20% or less of the total particle volume. The shell portion is preferably silver iodochloride or silver bromochloride. The shell part preferably contains 0.5 mol% to 10 mol% of silver bromide, particularly preferably 1 mol% to 5 mol%, and the silver bromide content in all grains is preferably 5 mol%. The following are preferable, and 3 mol% or less is especially preferable.

  The grain size of the photosensitive silver halide may be fine grains having a size of 0.2 μm or less, or may be large grains having a projected diameter area of 10 μm or more. However, in order to obtain good graininess, the fine grains may be fine grains. preferable. The dispersibility may be polydispersed or monodispersed, but is preferably monodispersed.

In the present invention, an iridium complex or an iridium ion-containing compound can be preferably used. The iridium ion-containing compound is a trivalent or tetravalent salt or complex salt, and a complex salt is particularly preferable. For example, primary iridium (III) chloride, primary iridium bromide (III), secondary iridium chloride (IV), sodium hexachloroiridium (III), potassium hexachloroiridium (IV), hexaammine iridium (IV) salt , Halogens such as trioxalatoiridium (III) salt and trioxalatoiridium (IV) salt, amines, and oxalato complex salts are preferable. The amount of the iridium complex or the iridium ion-containing compound is preferably 1.0 × 10 ⁻⁸ mol / silver or more and 5.0 × 10 ⁻⁶ mol / silver or less, more preferably 2 with respect to the amount of silver halide. It is preferable that it is 0.0 × 10 ⁻⁸ mol / silver or more and 2.5 × 10 ⁻⁶ mol / silver or less.

  The iridium complex or the iridium ion-containing compound may be contained in the core part, the shell part, or the uniform part of the silver halide grains, and a portion having a different halogen composition is grown at the corner part by heterojunction. Although it can also be selectively contained, it is not particularly limited.

The photosensitive silver halide grain of the present invention may contain at least one metal complex selected from rhodium, rhenium, ruthenium, osnium, cobalt, mercury, or iron in addition to the iridium complex or the iridium ion-containing compound. it can. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred metal content is preferably in the range of 1 × 10 ⁻⁹ mol / silver mol to 1 × 10 ⁻³ mol / silver mol per mol of silver, preferably 1 × 10 ⁻⁹ mol / silver mol to 1 × 10 ^−4. As a specific metal complex structure in which the range of mole / silver mole is more preferable, for example, a metal complex having a structure described in JP-A-7-225449 can be used. As the cobalt and iron complex, a 6-cyano metal complex can be preferably used.

  The photosensitive silver halide grain of the present invention is preferably chemically sensitized. As a preferred chemical sensitization method, as well known in the art, a chalcogen compound (sulfur compound, selenium compound, tellurium compound) sensitization method, a gold compound, a noble metal sensitization method such as platinum, palladium, iridium compound, etc. Alternatively, a reduction sensitization method can be used. Furthermore, spectral sensitization can also be used. The additive used in this step is RD No. No. 17643, ibid. No. 18716 and the same No. The compounds described in No. 307105 can be preferably used.

  The silver halide color photographic light-sensitive material of the present invention preferably contains a solid fine particle dispersion of a dye. As specific compounds and preparation methods, for example, compounds described in JP-A-2004-37534 can be preferably used.

The photographic additives that can be used or used in the present invention are described in the following Research Disclosure Journal (RD), and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1) Chemical sensitizer, page 23, page 648, right column, page 866 2) Sensitivity enhancer, page 648, right column 3) Spectral sensitizer, page 23-24, page 648, right column, page 866-868 Supersensitizer, page 649 Right column 4) Brightening agent page 24 647 page right column 868 page 5) Light absorber, page 25-26 Page 649, right column page 873 Filter dye, ~ 650 page, right column UV absorber 6) Binder page 26, page 651, left Column 873-874 page 7) plasticizer, lubricant 27 page 650 page right column 876 page 8) coating aid, page 26-27 page 650 right column page 875-876 surface active agent 9) antistatic agent page 27 page 650 Right column, pages 876 to 877 10) Matting agent, pages 878 to 879

  In the silver halide color photographic light-sensitive material of the present invention, various dye-forming couplers can be used, but the following dye-forming couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of European Patent EP502,424A; couplers represented by formulas (1) and (2) of European Patent EP513,496A (particularly Y on page 18) -28); couplers represented by general formula (I) of claim 1 of JP-A-5-307248; general formula (I) of lines 45 to 55 of column 1 of US Pat. No. 5,066,576 A coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; a coupler described in claim 1 on page 40 of European Patent EP498,381A1 (particularly D on page 18). -35); couplers represented by formula (Y) on page 4 of European Patent EP447,969A1 (particularly Y-1 (page 17), Y-54 (page 41)); US Pat. No. 4,476,219 Column 7 of 36 58 rows of formula (II) couplers represented by ~ (IV) (particularly II-17, 19 (column 17), II-24 (column 19)).

  Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-68 (page 12, lower right), L-77 (page 13, lower right)); European Patent EP456,257, A- 4-63 (page 134), A-4-73, -75 (page 139); European Patent EP486,965, M-4, -6 (page 26), M-7 (page 27); No. 43611, paragraph 0024 M-45, JP-A-5-204106, paragraph 0036 M-1; JP-A-4-36263, paragraph 0237 M-22. Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14-16) of JP-A-4-204843; C-7,10 (page 35) of JP-A-4-43345 , 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Coupler. Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345. Infrared coupler for forming a sound track: couplers described in JP-A No. 63-143546 and publications cited therein.

  Examples of couplers in which the coloring dye has an appropriate diffusibility are described in US Pat. No. 4,366,237, German Patent GB 2,125570, European Patent EP 96,873B, German Patent DE 3,234,533. Those are preferred. A coupler for correcting unwanted absorption of a coloring dye is a yellow colored cyan coupler represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of European Patent EP456,257A1. (Especially YC-86 on page 84), yellow colored magenta coupler ExM-7 (page 202, EX-1 (page 249), EX-7 (page 251), US Pat. No. 069, magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10), US Pat. No. 4,837,136 (2) (column 8), the formula of claim 1 of International Publication WO92 / 11575 A colorless masking coupler represented by [C-1] (especially the exemplified compounds on pages 36 to 45) is preferred.

  Examples of compounds (including dye-forming couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: a compound represented by any one of formulas (I), (II), (III) and (IV) described on page 11 of European Patent EP378,236A1 (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, 938A2 Compounds represented by formula (I) described on page 7 (especially D-49 (page 51)), compounds represented by formula (1) of JP-A-5-307248 (particularly paragraph (0027) of paragraph 0027) A compound represented by any one of formulas (I), (II) and (III) described on pages 5 to 6 of European Patent EP440,195A2 (particularly I- (1) on page 29); Release compounds: Formula (I), (I) on page 5 of EP 310,125A2 ) (Especially (60) and (61) on page 61) and the compound represented by formula (I) in claim 1 of JP-A-6-59411 (particularly paragraph (0022) (7)); Ligand-releasing compound: Compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (especially the compound on lines 21 to 41 of column 12); leuco dye releasing compound; US Pat. , 749,641 columns 3-8 compounds 1-6; fluorescent dye-releasing compounds: compounds represented by COUP-DYE of claim 1 of US Pat. No. 4,774,181 (especially compounds of columns 7-10) 1-11); development accelerator or fogging agent releasing compound: compound represented by formulas (1), (2), (3) of column 3 of U.S. Pat. No. 4,656,123 (especially ( I-22)) and European patents ExZK-2 on page 75, lines 36-38 of P450, 637A2; a compound that releases a group that becomes a dye only after leaving: represented by the formula (I) of claim 1 of US Pat. No. 4,857,447 Compound (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 of JP-A-62-215272 (140- 144); Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidant scavenger for developing agent: Rows 54 to 62 of column 2 of US Pat. No. 4,978,606 Of the compound represented by formula (I) (particularly I- (1), (2), (6), (12) (columns 4 to 5), column 2 of US Pat. No. 4,923,787 Line 10 to 10 (especially compound 1 (column 3); stain inhibitor: European Patent EP 298321A, page 4, lines 30 to 33, formulas (I) to (III), especially I-47, 72, III-1, 27 (pages 24 to 48); antifading agent: European Patent E 298321A A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69-118), US Patent No. Nos. 5,122,444, columns 25-38, II-1 to III-23, especially III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-2, US patent. No. 5,139,931, columns A1 to 48, particularly A-39,42 of columns 32 to 40; material for reducing the amount of color-enhancing agent or color mixing inhibitor used: pages 5 to 24 of European Patent No. EP411324A I-1 to II-15, especially I-46; formalin scavenger: pages 24 to 29 of European Patent EP 477932A, SCV-1 to 28, especially SCV-8;

  Hardener: Formulas (VII) to (XII) in columns 13 to 23 of H-1,4,6,8,14, US Pat. No. 4,618,573, page 17 of JP-A-1-214845 Compound (H-1 to 54), compound (H-1 to 76) represented by formula (6) at the lower right of page 8 of JP-A-2-214852, particularly H-14, US Pat. , 325,287, Claim 1; Development inhibitor precursor: JP-A 62-168139, P-24, 37, 39 (pages 6-7); US Pat. No. 5,019,492 Compounds according to claim 1, in particular 28 to 29 in column 7, preservatives, fungicides: U.S. Pat. No. 4,923,790, columns 3 to 15, I-1 to III-43, in particular II-1. 9, 10, 18, III-25; stabilizer, antifoggant: US Pat. No. 4,92 793, columns 6-16 of I-1 to (14), in particular I-1,60, (2), (13), US Pat. No. 4,952,483, compounds 25 to 32 of compounds 1 to 1 65, especially 36: chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; usable 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 27 to 29, V-1 to 23, especially V-1, EP 445627A, pages 33 to 55, FI- 1-F-II-43, especially F-I-11, F-II-8, European Patent EP 457153A, pages 17-28, III-I to 36, especially III-1,3, International Publication WO 88/04794 8 to 26 Dye-1 to 124 microcrystalline dispersion, Europe Patents EP319999A, pages 6-11, compounds 1-22, especially compound 1, compounds D-1 to 87 represented by formulas (1) to (3) in EP519306A (pages 3 to 28), US patent Nos. 4,268,622, compounds 1-22 (columns 3-10) represented by formula (I), U.S. Pat. No. 4,923,788, compounds represented by formula (I)- (31) (columns 2 to 9); UV absorber: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) of JP-A No. 46-3335, Europe Patents EP320938A compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds represented by formula (III) HBT-1 to HBT-10 (page 14), European Patent Compounds (1) to (31) represented by the formula (1) in EP521823 (Columns 2-9).

  The silver halide color photographic light-sensitive material of the present invention contains fluorine atoms in the layer farthest from the support having the emulsion layer or the layer farthest from the support having no emulsion layer, or both. A compound can be preferably used. Of these, the compounds described in JP-A No. 2003-114503 are preferably used.

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 T1 _{/ 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 at 35 ° C. for 3 minutes with a color developer is defined as the saturated film thickness. To do. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is photographic science and engineering by A. Green et al. (Photogr. Sci. Eng), Vol. 19, pages 2, 124-129. T _1/2 can be adjusted 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 the amount of equilibrium swelling when the silver halide photographic light-sensitive material of the present invention is immersed in distilled water at 35 ° C. to swell, 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.

  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; 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. The non-photosensitive layer of the present invention is preferably hardened, and examples of the hardener include aziridines, triazines, vinyl sulfones, aldehydes, cyanoacrylates, peptides, epoxies, and melamines. Although used, a melamine compound is particularly preferable from the viewpoint of firmly fixing the conductive metal oxide particles.

Examples of the conductive metal oxide particle material include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ and V ₂ O _5, and composite 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 should 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 holmar, 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 surfactant, a slipping agent and the like. Examples of the matting agent include oxides such as silicon oxide, aluminum oxide, and magnesium oxide having a particle diameter of 0.001 to 10 μm, and polymers or copolymers such as polymethyl methacrylate and polystyrene.

  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.
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Preparation of blue-sensitive layer emulsion BH-1)
High silver chloride cubes by mixing silver nitrate, sodium chloride, and potassium bromide (0.5 mol% per mol of the finished silver halide) with deionized distilled water containing stirred deionized gelatin. Particles were prepared. In the course of this preparation, K ₂ [IrCl ₅ (5-methylthiazole)] was added from 60% to 80% addition of silver nitrate. K ₄ [Fe (CN) ₆ ] was added from the time point when the addition of silver nitrate was 80% to 90%. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from 83% to 88% addition of silver nitrate. When 94% of the addition of silver nitrate was completed, potassium iodide (0.27 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodisperse cubic silver bromochloride grains having a side length of 0.50 μm, a coefficient of variation of 8.5%, and a silver chloride content of 97 mol%. This emulsion was subjected to precipitation desalting treatment, and gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added thereto and redispersed.

The redispersed emulsion was dissolved at 40 ° C., and sensitizing dye S-1, sensitizing dye S-2, and sensitizing dye S-3 of the present invention were added so as to optimize spectral sensitization. Next, sodium benzenethiosulfate, triethylthiourea as a sulfur sensitizer, and compound-1 as a gold sensitizer were added and ripened so as to optimize chemical sensitization. Thereafter, 1- (5-acetamidophenyl) -5-mercaptotetrazole, a compound having repeating unit 2 or 3 represented by compound-2 as a main component (terminal X ₁ and X ₂ are hydroxyl groups), compound-3 and odor Potassium hydride was added to complete the chemical sensitization. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of blue-sensitive layer emulsion BM-1)
In the preparation of Emulsion BH-1, the temperature and rate of addition of silver nitrate, sodium chloride and potassium bromide (0.5 mol% per mol of the finished silver halide) were mixed and mixed, and silver nitrate and chloride were changed. Emulsion grains were obtained in the same manner except that the amount of various metal complexes added during the addition of sodium and potassium bromide was changed. The emulsion grains were monodisperse cubic silver iodobromochloride grains having a side length of 0.41 μm, a coefficient of variation of 9.5%, and a silver chloride content of 97 mol%. After redispersion of this emulsion, Emulsion BM-1 was similarly prepared except that the amount of various compounds added was changed from Emulsion BH-1 to the same amount per unit area.

(Preparation of blue-sensitive layer emulsion BL-1)
In the preparation of Emulsion BH-1, the temperature and rate of addition of silver nitrate, sodium chloride and potassium bromide (0.5 mol% per mol of the finished silver halide) were mixed and mixed, and silver nitrate and chloride were changed. Emulsion grains were obtained in the same manner except that the amount of various metal complexes added during the addition of sodium and potassium bromide was changed. The emulsion grains were monodisperse cubic silver iodobromochloride grains having a side length of 0.29 μm, a coefficient of variation of 9.7%, and a silver chloride content of 97 mol%. After redispersion of this emulsion, Emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from Emulsion BH-1 to the same amount per unit area.

  When the iodine distribution in the grains of each of the emulsions BH-1, BM-1, and BL-1 was confirmed by the method described in the detailed description, the concentration of iodide ions was increased toward the inside. It was confirmed that was attenuated.

(Preparation of comparative blue-sensitive emulsions BH-2, BM-2, BL-2)
Blue-sensitive emulsions BH-2 and BM were all prepared in the same manner as in the preparation of BH-1, BM-1 and BL-1, except that equimolar sodium chloride was used instead of potassium iodide used for grain formation. -2 and BL-2 were prepared. The grain size, coefficient of variation, and silver chloride content were the same as BH-1, BM-1, and BL-1.

(Preparation of blue-sensitive layer emulsion BH-3 for comparison)
46.4 ml of a 10% solution of NaCl is added to 1.08 liters of deionized distilled water containing 5.7% by weight of deionized gelatin, and 46.4 ml of H ₂ SO ₄ (1N) is further added. After adding 0.013 g of the compound represented by X) and adjusting the liquid temperature to 62 ° C., immediately adding 0.1 mol of silver nitrate and 0.1 mol of NaCl to the reaction vessel over 15 minutes while stirring at high speed. did. Subsequently, 1.5 mol of silver nitrate and NaCl solution were added over 50 minutes by the flow rate acceleration method so that the final addition rate was 4 times the initial addition rate. Next, 0.2 mol% silver nitrate and NaCl solution were added at a constant addition rate over 6 minutes. At this time, to the NaCl solution, K ₃ IrCl ₅ (H ₂ O) was added in an amount of 9 × 10 ⁻⁷ mol with respect to the total silver amount, and iridium aquodide was doped into the particles.
Further, 0.2 mol of silver nitrate, 0.18 mol of NaCl, and 0.02 mol of KBr solution were added over 10 minutes. At this time, K ₄ Ru (CN) ₆ and K ₄ Fe (CN) ₆ corresponding to 0.7 × 10 ⁻⁵ mol with respect to the total silver amount were dissolved in the halogen aqueous solution and added to the silver halide grains. did.
Thereafter, a precipitation agent of compound (Y) was added at 40 ° C., and the pH was adjusted to around 3.5, followed by desalting and washing with water.

  Deionized gelatin, an aqueous NaCl solution and an aqueous NaOH solution were added to the emulsion after washing with desalted water, and the mixture was heated to 50 ° C. and adjusted to pAg 7.6 and pH 5.6. Thus, a silver halide having an average side length of 0.80 μm and a side length variation coefficient of 9%, comprising a halogen composition of 98.9 mol% of silver chloride, 1 mol% of silver bromide, and 0.1 mol% of silver iodide. Cubic particles were obtained.

The emulsion grains were maintained at 60 ° C., and spectral sensitizing dyes 1 and 2 were added at 2.4 × 10 ⁻⁴ mol / Ag mol and 2.2 × 10 ⁻⁴ mol / Ag mol, respectively. Further, a fine grain emulsion obtained by adding 1.5 × 10 ⁻⁵ mol / Ag mol of thiosulfonic acid compound-1 and doping iridium hexachloride with 90 mol% of silver bromide and 10 mol% of silver chloride having an average grain diameter of 0.05 μm. And aged for 10 minutes. Further, fine grains of silver bromide 40 mol% and silver chloride 60 mol% having an average grain size of 0.05 μm were added and ripened for 10 minutes. The fine particles were dissolved, thereby increasing the silver bromide content of the host cubic grains to 0.013 moles per mole of silver. Further, iridium hexachloride was doped with 1 × 10 ⁻⁷ mol / Ag mol.

Subsequently, 1 × 10 ⁻⁵ mol / Ag mol of sodium thiosulfate and 2 × 10 ⁻⁵ mol of gold sensitizer-1 were added. Immediately after that, the temperature was raised to 60 ° C., followed by aging for 40 minutes, and then the temperature was lowered to 50 ° C. Immediately after the temperature was lowered, mercapto compounds-1 and 2 were added so as to be 6.3 × 10 ⁻⁴ mol / Ag mol, respectively. Thereafter, after ripening for 10 minutes, the KBr aqueous solution was added to 0.008 mol with respect to silver, and after aging for 10 minutes, the temperature was lowered and stored. In this way, high-sensitivity emulsion BH-3 having a silver chloride content of 97.8 mol% was prepared.

(Adjustment of blue-sensitive layer emulsion BL-3 for comparison)
Cubic grains having an average side length of 0.52 μm and a side length coefficient of variation of 9% were formed in exactly the same manner except for the emulsion preparation method of BH-3 and the temperature during grain formation. The temperature during grain formation was 55 ° C.
Spectral sensitization and chemical sensitization were carried out in an amount that was corrected to match the specific surface area (side length ratio 0.8 / 0.52 = 1.54 times), and the silver chloride content was as low as 97.8 mol%. Sensitivity emulsion BL-3 was prepared.

(Preparation of red-sensitive silver halide emulsion grains)
A silver chlorobromide emulsion each having a cubic shape, a large emulsion grain R11 having an average grain size of 0.23 μm, a medium emulsion grain R21 having an average grain size of 0.174 μm, and a small emulsion grain R31 having an average grain size of 0.121 μm, Coefficients of variation in grain size distribution were 0.11, 0.12, and 0.13, respectively. Emulsion grains having a halogen composition of Br / Cl = 8/92 were both silver nitrate by a control double jet method known in the art. And a mixture of sodium chloride and potassium bromide was added. The iridium content was adjusted to 3 × 10 ⁻⁷ mol / silver. In this emulsion grain, the red-sensitive sensitizing dye (D) shown below is 2.1 × 10 ⁻ per mol of silver for each of large emulsion grains R11, medium emulsion grains R21 and small emulsion grains R31. ⁵ mol, 3.3 × 10 ⁻⁵ mol, 4.5 × 10 ⁻⁵ mol, and sensitizing dye (E) 1.8 × 10 ⁻⁵ mol, 2.3 × 10 ⁻⁵ mol, 3.6 respectively × 10 ⁻⁵ mol, and further a sensitizing dye (F) was added in an amount of 0.8 × 10 ⁻⁵ mol, 1.4 × 10 ⁻⁵ mol, and 2.1 × 10 ⁻⁵ mol, respectively. The chemical ripening of these emulsions was optimally performed by adding a sulfur sensitizer and a gold sensitizer. Further, the following compound 1 is 9.0 × 10 ⁻⁴ mol, 1.0 × 10 ⁻³ mol, and 1.4 × 10 ⁻³ mol per mol of silver with respect to silver halide emulsion grains R11, R21, and R31. Mole was added.

(Preparation of green sensitive silver halide emulsion grains)
A silver chlorobromide emulsion each having a cubic shape, a large emulsion grain G11 having an average grain size of 0.20 μm, a medium emulsion grain G21 having an average grain size of 0.146 μm, and a small emulsion grain G31 having an average grain size of 0.102 μm, Emulsion grains having a grain size distribution variation coefficient of 0.11, 0.12, and 0.10 and a halogen composition of Br / Cl = 3/97 were prepared. The iridium content was adjusted to 3 × 10 ⁻⁷ mol / silver. With respect to the emulsion grains, the following green-sensitive sensitizing dye (G) is 2.1 × 10 ⁻⁴ mol and 3.0 × 10 ⁻⁴ mol with respect to G11, G21 and G31, respectively, per mol of silver. 3.5 × 10 ⁻⁴ mol, sensitizing dye (H) 0.8 × 10 ⁻⁴ mol, 1.3 × 10 ⁻⁴ mol, 1.7 × 10 ⁻⁴ mol, sensitizing dye (I) ) ^Is 1.2 × 10 ⁻⁴ mol, 1.4 × 10 ⁻⁴ mol, 1.9 × 10 ⁻⁴ mol, and sensitizing dye (J) is 0.3 × 10 ⁻⁴ mol, 0.6 respectively. × 10 ⁻⁴ mol and 0.9 × 10 ⁻⁴ mol were added. The chemical ripening of these emulsions was optimally performed by adding a sulfur sensitizer and a gold sensitizer.

(Preparation of photosensitive silver halide emulsion grains for bleach-inhibitor-releasing coupler-containing layer)
Each of silver chlorobromide emulsions, each of which is cubic, has a large size emulsion grain SH-1 having an average grain size of 0.30 μm, a medium size emulsion grain SM-1 having an average grain size of 0.23 μm, and a small size having an average grain size of 0.15 μm. Emulsion grains SL-1, emulsion grains having a grain size distribution variation coefficient of 0.09, 0.10 and 0.12, respectively, and a halogen composition of Br / Cl = 10/90 are known in the art. It was prepared by adding a mixture of silver nitrate, sodium chloride and potassium bromide by a controlled double jet method. The iridium content was adjusted to 3 × 10 ⁻⁷ mol / silver. The chemical ripening of the emulsion grains was optimally performed by adding a sulfur sensitizer and a gold sensitizer. Further, the above compound 1 is 9.0 × 10 ⁻⁴ mol, 1.0 × 10 ⁻³ mol, 1 × 10 ⁻³ mol per 1 mol of silver with respect to silver halide emulsion grains SH-1, SM-1, and SL-1. 4 × 10 ⁻³ mol was added.

(Preparation of emulsion dispersion Y for yellow photosensitive layer)
A material having the following constitution was dissolved and mixed, and emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 80 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion Y.
Yellow coupler (ExY) 116.0g
Additive 1 8.8g
Additive 2 9.0g
Additive 3 4.8 g
Additive 4 10.0g
Solvent 1 79.0 g
Solvent 2 44.0 g
Solvent 3 9.0g
Solvent 4 4.0 g
Ethyl acetate 150.0ml

(Preparation of emulsion dispersion M for magenta photosensitive layer and emulsion dispersion C for cyan photosensitive layer)
Similarly to the preparation of the emulsified dispersion Y, magenta and cyan photosensitive layer emulsified dispersions M and C were prepared using a magenta coupler (ExM) and a cyan coupler (ExC), respectively.

(Preparation of Bleach Inhibitor-Releasing Coupler-Containing Dispersion S)
In the same manner as the preparation of the emulsion dispersion Y, a bleach inhibitor releasing coupler-containing emulsion S was prepared using the following bleach inhibitor releasing coupler (ExB).
Bleach inhibitor releasing coupler (ExB) 55.0g
Additive 2 9.0g
Additive 3 4.8 g
Additive 4 10.0g
Solvent 1 79.0 g
Solvent 2 44.0 g
Solvent 3 9.0g
Solvent 4 4.0 g
Ethyl acetate 150.0ml

(Preparation of dye solid fine particle dispersion A)
The methanol wet cake of the following dye 1 was weighed so that the net amount of the compound was 240 g, 48 g of the following compound 2 was weighed as a dispersion aid, and water was added to make 4000 g. “Flow-through sand grinder mill (UVM-2)” (manufactured by IMEX KK) is filled with 1.7 liters of zirconia beads (0.5 mm diameter), discharge amount is 0.5 liter / min, and peripheral speed is 10 m / minute. Milled for 2 hours at sec. Thereafter, the dispersion was diluted so that the compound concentration was 3% by mass. Thereafter, heat treatment was performed at 90 ° C. for 10 hours. Thus, the preparation of Dispersion A was completed. The average particle size of this dispersion was 0.45 μm.

(Preparation of yellow photosensitive emulsion layer coating solution)
The type and blend ratio of the blue-sensitive emulsion were silver molar ratios used as described in Table 1, and the other materials were dissolved and mixed at the following ratios to obtain a yellow photosensitive emulsion layer coating solution. Numbers are given in units of g / m ² . The coating amount of the emulsion was a silver conversion coating amount. The yellow coupler was used in the form of dispersion Y, and the numbers were shown as the amount of coupler used.
Silver halide emulsion 0.49
Yellow coupler (EXY) 1.18
Gelatin 2.10
Compound 3 0.0005
Compound 4 0.03
Compound 5 0.04

(Preparation of magenta photosensitive emulsion layer coating solution)
In the same manner as the yellow photosensitive layer coating solution, an emulsion and a material having the following composition were mixed and dissolved to obtain a magenta photosensitive emulsion layer. The coating amount of the emulsion was a silver conversion coating amount. The mixing ratio of the green sensitive silver halide emulsion was 1: 3: 6 in terms of silver molar ratio. The magenta coupler was used in the form of dispersion M, and the numbers were shown as the amount of coupler used.
Green sensitive silver halide emulsion
G11: G21: G31 0.55
Magenta coupler (ExM) 0.68
Gelatin 1.28

(Preparation of cyan photosensitive emulsion layer coating solution)
In the same manner as the yellow photosensitive layer coating solution, emulsions and materials having the following composition were mixed and dissolved to form a cyan photosensitive emulsion layer. The coating amount of the emulsion was a silver conversion coating amount. The mixing ratio of the red-sensitive silver halide emulsion was 2: 3: 5 in terms of silver molar ratio. The cyan coupler was used in the form of Dispersion C, and the numbers were expressed as the amount of coupler used.
Red-sensitive silver halide emulsion
R11: R21: R31 0.46
Cyan coupler (ExC) 0.72
Dye 1 0.02
Gelatin 2.45

(Create an antihalation layer)
The dye solid fine particle dispersion A prepared as described above was mixed and dissolved so that the amount of gelatin applied was 0.11 g / m ² and the amount of gelatin applied was 0.70 g / m ² to prepare a coating solution for a halation prevention layer.

(Middle layer creation)
The following gelatin and chemicals were dissolved and mixed.
Gelatin 0.67
Compound 6 0.04
Compound 7 0.02
Solvent 5 0.01

(Creation of protective layer)
The following gelatin and chemicals were dissolved and mixed.
Gelatin 0.96
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.02
Compound 8 0.04
Compound 9 0.013

(Preparation of a layer containing a bleach inhibitor releasing coupler)
In the same manner as the yellow photosensitive layer coating solution, an emulsion and a material having the following composition were mixed and dissolved to obtain a bleach inhibitor releasing coupler-containing layer. The coating amount of the emulsion was a silver conversion coating amount. The mixing ratio of the silver halide emulsion for the bleach inhibitor releasing coupler-containing layer was 2: 3: 5 in terms of silver molar ratio. The bleach inhibitor releasing coupler was used in the form of Dispersion S, and the numbers were expressed as the amount of coupler used.
Photosensitive silver halide emulsion grain for bleach-inhibitor-releasing coupler-containing layer SH-1: SM-1: SL-1 0.97
Bleach inhibitor releasing coupler (ExB) 0.13
Gelatin 2.45

As a curing agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The amount used was adjusted so that the swelling value obtained from the following formula was 200%.
Swelling rate = 100 × (maximum swollen film thickness−film thickness) ÷ film thickness (%)
The following dyes 2 to 5 were added to the emulsion layer for the purpose of preventing irradiation.

(Create support)
Acrylic resin layer containing a biaxially stretched polyethylene terephthalate support the following conductive polymer on one side of (0.05 g / ^{m 2)} and tin oxide fine particles (0.20 g / ^{m 2)} having a thickness of 120μm was coated.

(Preparation of coated sample 1)
The coating solution prepared as described above was coated and dried by the simultaneous extrusion method so that the anti-halation layer was the bottom layer on the opposite side of the polyethylene terephthalate support on which the acrylic layer resin was coated, and dried. It was created. A coated sample 2 in which the silver halide grains of the yellow photosensitive layer were changed was similarly prepared.
Protective layer
Magenta photosensitive layer
Middle class
Cyan photosensitive layer
Middle class
Yellow photosensitive layer
Antihalation layer
Polyethylene terephthalate support

(Preparation of coating sample 3)
In the preparation of the coated sample 1, the bleach-inhibitor coupler-containing layer prepared as described above was inserted between the protective layer and the magenta photosensitive layer. The layer structure is shown below.
Protective layer
Bleach inhibitor releasing coupler containing layer
Middle class
Magenta photosensitive layer
Middle class
Cyan photosensitive layer
Middle class
Yellow photosensitive layer
Antihalation layer
Polyethylene terephthalate support

  As shown in Table 1 below, coated samples 1 to 5 were prepared.

(Preparation of processing solution)
An ECP-2 process published by Eastman Kodak Company was prepared as a standard processing method for projection film. For all the prepared samples, an image was developed so that about 30% of the applied silver amount was developed. The exposed sample was subjected to continuous processing (running test) in the above-described processing process until the replenisher amount in the color developer bath doubled the tank capacity, and a development processing state in running equilibrium was prepared.

ECP-2 process <Process>
Process name Processing temperature (℃) Processing time (seconds) Replenishment amount
(per ml 35mm x 30.48m)
1. Prebus 27 ± 1 10-20 400
2. Water wash 27 ± 1 Jet water wash −
3. Development 36.7 ± 0.1 180 690
4). Stop 27 ± 1 40 770
5. Washing with water 27 ± 3 40 1200
6). First fixing 27 ± 1 40 200
7). Washing with water 27 ± 3 40 1200
8). Bleaching acceleration 27 ± 1 20 200
9. Bleaching 27 ± 1 40 200
10. Washing with water 27 ± 3 40 1200
11. Drying 12. SOUN Room temperature 10-20-(Painting)
Development 13. Washing water 27 ± 3 1-2-(spray)
14 Second fixing 27 ± 1 40 200
15. Washing with water 27 ± 3 60 1200
16. Rinse 27 ± 3 10 400
<Processing liquid formulation>
Shows the composition per liter. Process name Chemical name Tank liquid Replenisher Prevas Borax 20g 20g
Sodium sulfate 100g 100g
Sodium hydroxide 1.0g 1.5g
Development Kodak
Anticalcium No. 4 1.0ml 1.4ml
Sodium sulfite 4.35g 4.50g
CD-2 2.95 g 6.00 g
Sodium carbonate 17.1g 18.0g
Sodium bromide 1.72 g 1.60 g
Sodium hydroxide-0.6g
Sulfuric acid (7N) 0.62 ml −
Stop Sulfuric acid (7N) 50ml 50ml
Fixing (Common for first and second) Ammonium thiosulfate (58%) 100ml 170ml
Sodium sulfite 2.5g 16.0g
Sodium bisulfite 10.3g 5.8g
Potassium iodide 0.5g 0.7g
Bleaching acceleration Sodium metabisulfite 3.3g 5.6g
Acetic acid 5.0 ml 7.0 ml
Bleaching accelerating aid (PBA-1) 3.3 g 4.9 g
Perdicate bleach accelerator by Kodak
EDTA-4Na 0.5g 0.7g
Bleach gelatin 0.35g 0.50g
Sodium persulfate 33g 52g
Sodium chloride 15g 20g
Sodium dihydrogen phosphate 7.0 g 10.0 g
Phosphoric acid (85%) 2.5ml 2.5ml
Sound Natrosa1250HR 2.0g
developing
Sodium hydroxide 80g
Hexyl glycol 2.0ml
Sodium sulfite 60g
60 g of hydroquinone
Ethylenediamine (98%) 13ml
Rinse stabilizer 0.14ml 0.17ml
Rinse aid [Dearside
(Dearcide) 702] 0.7ml 0.7ml
In the above, CD-2 used in the developing step is a developing agent (4-amino-3-methyl-N, N-dimethylaniline), and Decarcide 702 used in the rinsing step is an antifungal agent.

(Cross modulation test)
In order to use the appropriate concentration of sound negative, a cross-modulation test was performed on each coated sample. The cross modulation signal used was 7 kHz modulated at 400 Hz. The sound baking density of each sample was set to 1.3 in terms of the infrared absorption density of a Macbeth TD206A type densitometer. For the coated samples 3 to 5, among the processing solutions prepared as described above, the sound development processing (coating) and the subsequent water washing step were omitted. Under the above conditions, the optimum sound negative density for each coated sample was determined. The audio signal was burned onto each coated sample from a sound negative burned at a concentration optimized for each sample based on the results of this test.

(Sound test)
For the photosensitive material of the present invention, a filter for cutting light having a wavelength of 400 nm to 600 nm for preparing an infrared sound track was prepared. For each of the coated samples 1 to 5, the sound negative optimized for each sample as described above was recorded with white light transmitted through the prepared filter and modulated at 400 Hz, and the coated sample was brought into close contact with each other. The signal was exposed and processed with the processing solution prepared as described above. At this time, the sound development process and the subsequent water washing process were performed or omitted, as shown in Table 1. With respect to the treated coated sample, sound was reproduced with a projector (CINEFORWARD FC-10 manufactured by Fuji Photo Film). At this time, relative evaluation was performed with ± 0 dB as a result of an experiment in which sound development and subsequent water washing process were performed on the coated sample 1.

(Evaluation of photographic performance of blue photosensitive layer)
Using a sensitometer (FW type manufactured by Fuji Photo Film Co., Ltd., light source color temperature 3200K), exposure is performed so that a neutral gray sensitometric image can be obtained through yellow and magenta color correction filters and an optical wedge. Using the processing solution prepared as described above, the color development processing time is 180 seconds, and the reciprocal of the ratio of the exposure amount that gives the density of the yellow color density of 1.0 higher than that of the coating sample 1 as a reference. Photosensitivity was evaluated at a value multiplied by 100.

(Evaluation of development progress of blue photosensitive layer)
Subsequently, the exposure performed in the evaluation of the photographic performance described above and the brown development processing time of 120 seconds in the processing prepared as described above were performed, and the photographic sensitivity was evaluated at the developing time of 120 seconds as in the evaluation of the photographic performance. did. For each sample, with respect to a value obtained by multiplying the reciprocal of the exposure amount ratio giving a photographic sensitivity at a brown development processing time of 180 seconds with reference to an exposure amount giving a photographic sensitivity at a brown development processing time of 120 seconds, a coated sample Evaluation was made as a relative value when 1 was 100.

  The results are shown in Table 2.

  As can be seen from Table 2, the coated sample having the bleach-inhibiting agent-releasing coupler-containing layer can reproduce a good analog sound even if the applied sound track development step is omitted. Moreover, the average grain size of the yellow photosensitive silver halide is 0.4 μm or less, the silver chloride content is 95 mol% or more with respect to the total silver amount, and iodide ions have a maximum concentration on the grain surface and are directed inward. By using photosensitive silver halide grains with a reduced iodide ion concentration, it was confirmed that although it was small in size, it had high sensitivity and rapid development progress, and the processing time could be shortened. .

(Preparation of blue-sensitive silver halide emulsion grains BH-4)
Sodium chloride 1.3 g was added to a 2% aqueous solution of lime-processed gelatin, and acid was added to adjust the pH to 4.3. An aqueous solution containing 0.03 mol of silver nitrate and an aqueous solution containing 0.03 mol of sodium chloride and potassium bromide were added and mixed at 41 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.005 mol of potassium bromide was added, and then an aqueous solution containing 0.13 mol of silver nitrate and an aqueous solution containing 0.12 mol of sodium chloride were added. Further, while raising the temperature to 72 ° C. and maintaining pAg at 7.2, 3 × 10 ⁻⁷ mol of the aqueous solution containing 0.9 mol of silver nitrate, the aqueous solution containing 0.9 mol of sodium chloride, and the total silver amount The iridium compound K ₂ [IrCl ₅ (5-methylthiazole)] was added and mixed, and after another 5 minutes, an aqueous solution containing 0.1 mol of silver nitrate and an aqueous solution containing 0.1 mol of sodium chloride were added and mixed. After leaving for 40 minutes, it was washed with settled water at 35 ° C. to perform desalting. Thereafter, 110 g of lime-processed gelatin was added to adjust to Ph 5.9 and pAg 7.1. Thus, the main plane is a {100} plane tabular grain, the projected area equivalent diameter is 0.78 μm, the average thickness is 0.14 μm, the average aspect ratio is 4.7, and the equivalent to the side length of the cube is 0.39 μm, Tabular grains having a variation coefficient of 0.20 and a silver chloride content of 96.5 mol% were prepared. The following sensitizing dyes (A), (B), and (C) are 3.3 × 10 ⁻⁴ mol, 2.6 × 10 ⁻⁵ mol, and 1.5 × 10 ^{−5 to the} emulsion grains, respectively. It added so that it might become a mole. Thereafter, sulfur sensitizer and gold sensitizer were added to perform chemical ripening optimally, and preparation of blue-sensitive silver halide emulsion grains BH-4 was completed.

(Preparation of blue-sensitive silver halide emulsion grains BM-4)
In the preparation of the above BH-4, the potassium bromide of (X-1) was changed to 0.010 mol, the projected area equivalent diameter was 0.60 μm, the average thickness was 0.13 μm, the average aspect ratio was 3.8, the coefficient of variation. Tabular grains having a silver chloride content of 96.5 mol% of 0.22 were prepared. Sensitizing dyes (A), (B), and (C) were added in an amount of 4.8 × 10 ⁻⁴ mol, 4.5 × 10 ⁻⁵ mol, and 2.5 × 10 ⁻⁴ mol, respectively, and the same as for BH-4 Thus, chemical ripening was optimally carried out to complete the preparation of blue-sensitive silver halide emulsion grains BM-4.

(Preparation of blue-sensitive silver halide grains BL-4)
In the preparation of BH-4, the potassium bromide of (X-1) was changed to 0.014 mol, the projected area equivalent diameter was 0.40 μm, the average thickness was 0.12 μm, the average aspect ratio was 3.3, the coefficient of variation was Tabular grains having a silver chloride content of 96.5 mol% of 0.19 were prepared. Sensitizing dyes (A), (B), and (C) were added at 5.7 × 10 ⁻⁴ mol, 6.1 × 10 ⁻⁵ mol, and 3.3 × 10 ⁻⁴ mol, respectively. Chemical ripening was optimally performed in the same manner as BH-4, and preparation of blue-sensitive silver halide grains BL-4 was completed.

  In the coated sample 3 prepared in Example 1, BH-4, BM-4, and BL-4 newly prepared in place of the blue-sensitive silver halide BH-3 and BL-3 (both had an aspect ratio of 1) A coated sample 6 was prepared using an emulsion mixed at a silver molar ratio of 1: 3: 6. The coating amount of the emulsion was the same as that of the coating sample 3.

  In the same manner as the coated sample 3 of Example 1, a cross modulation test, a sound test, evaluation of photographic performance, and evaluation of development progress were performed. The results are shown in Table 3.

As apparent from Table 3, it was found that when tabular silver halide grains were used, the photographic sensitivity was high, the progress of development was fast, and the processing time could be shortened.

Claims (3)

  In a silver halide color photographic material having a yellow color developing photosensitive silver halide emulsion layer, a cyan color developing photosensitive silver halide emulsion layer, and a magenta color developing photosensitive silver halide emulsion layer on a transparent support, an oxidized form of a developing agent Photosensitive silver halide grains containing a compound that reacts with the compound to release a diffusion-resistant bleach inhibitor and is contained in the yellow color-forming photosensitive silver halide emulsion layer has an average grain size of 0.4 μm or less. In addition, the silver chloride content with respect to the total silver amount is 95 mol% or more, and the photosensitive silver halide grains have a maximum concentration of iodide ions on the grain surface, and the iodide ion concentration attenuates toward the inside. A silver halide color photographic light-sensitive material comprising photosensitive silver halide grains.   In a silver halide color photographic material having a yellow color developing photosensitive silver halide emulsion layer, a cyan color developing photosensitive silver halide emulsion layer, and a magenta color developing photosensitive silver halide emulsion layer on a transparent support, an oxidized form of a developing agent The photosensitive silver halide grains containing a compound that reacts with and releases a non-diffusible bleach inhibitor and is contained in the yellow color-forming photosensitive silver halide emulsion layer has a silver chloride content ratio relative to the total silver amount. A silver halide color photographic light-sensitive material comprising tabular photosensitive silver halide grains having an aspect ratio of 2 or more and having a mole ratio of 95 mol% or more. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the main plane of the tabular photosensitive silver halide grains is a {100} plane.