JP4115980B2 - Silver halide color photographic light-sensitive material and processing method - Google Patents

Description

  The present invention relates to a silver halide color photographic light-sensitive material that can be processed by a simplified and shortened exposure / processing step and a processing method thereof, and more particularly to a silver halide color photographic light-sensitive material for movies and a processing method thereof.

  Movie, which is an application of silver halide photography, is a method of obtaining a moving image by sequentially projecting 24 dense still images per second, and has an overwhelming image quality compared to other methods of reproducing moving images. Have. It is easy to make a large screen with its high image quality as a source, and it is suitable for a large number of people to watch moving images at the same time. Therefore, there are many theaters that can accommodate a large number of people with movie projection facilities such as movie theaters. However, recent rapid development of electronic technology and information processing technology has image quality close to that of movies using Texas Instruments DMD devices, Hughes-JVC D-ILA devices, Sony high-definition liquid crystal devices, etc. Thus, it has been possible to develop a projector that can provide a simpler means of reproducing a moving image. Accordingly, there is a need for movies to be provided with simplicity while maintaining the original high image quality, in particular, to simplify and shorten the time required for work at a developing station such as exposure and development.

One of the factors that complicates and makes the development of silver halide photographic light-sensitive materials for movie projection is the presence of sound development.
In movies, images and audio need to be synchronized. Since the invention of the movie, various attempts have been made to add audio to video. In particular, a combination with analog record technology, which is a voice recording / reproducing means invented at the same time, was examined, but the technology at that time could not be satisfactorily synchronized and was not widely put into practical use. In order to achieve simple and reliable synchronization, it is ideal that image information and audio information are simultaneously recorded on one projection film. From such a background, a technology for optically recording sound on a projection film was developed in the 1920s. At that time, B / W photographic light-sensitive materials for forming images with developed silver were the mainstream for projection films, and devices that read sound signals during projection were based on the premise that the signals were recorded as silver images. Since developed silver absorbs light in a wide range from ultraviolet light to infrared light, there is no particular restriction on the reading wavelength range of the reading device, and the maximum is around 800 nm to 900 nm, which was easy to put into practical use with the technology at that time. A sensitive device was used.

  Thereafter, in the silver halide color photographic light-sensitive material for projection that has been put to practical use, the coloring dye that forms a color image does not absorb in the near-infrared region of 800 to 900 nm used by the sound signal reader. However, the sound signal reading system has not been changed from the time of its development to the present day, and the sound signal is recorded as a silver image in the current halogen silver color photographic light-sensitive material for projection. On the other hand, in the silver halide color photographic light-sensitive material for projection, the developed silver is removed in the processing step because it is necessary to increase the color purity of the image area.

  Thus, in a silver halide color photographic light-sensitive material for projection, a dye image that does not require a silver image and a sound signal that must be formed of a silver image exist on the same material. For this reason, the development process of the silver halide color photographic light-sensitive material for projection is complicated, such as applying a special developer only to the part where the sound signal is recorded (so-called sound track) during the process, This is a heavy burden on the laboratory.

  On the other hand, the simplification of the development process is a very important issue from the viewpoint of environmental conservation through resource saving, in addition to reducing the burden on the development shop. Therefore, much research has been done and the results have been introduced into the market. For example, there were 14 standard development processes for negative-positive type silver halide color photographic light-sensitive materials for projection at the time of 1990 (development process published as ECP-2A by Eastman Kodak Company). By the improvement of the photosensitive material, it was shortened to 12 processes at the end of the 1990s (development process published as ECP-2D by Eastman Kodak Company). However, like the silver halide color photographic light-sensitive material for projection, the development process of silver halide color photographic paper for the purpose of image appreciation is only 3 steps, and from now on, it must be said that there are many current 12 steps. .

  One of the reasons for the large number of processing steps for the silver halide color photographic light-sensitive material for projection is the above-described complicated processing for the purpose of forming a sound track from the silver image. Therefore, a method for forming a sound track by the same processing steps as dye image formation has been studied.

  As a representative example, there is a method of forming a silver image sound track itself by using a bleach inhibitor releasing coupler typified by Patent Documents 1 to 13 to inhibit bleaching of a silver image imagewise.

  As another method, an infrared coloring coupler represented by Patent Documents 14 to 19 is used. This is a technology for forming a sound track with a coloring dye having absorption in the near infrared region required by an existing sound reader.

  As another means, there is a method of improving a sound signal reader so that a sound signal recorded with a coloring dye forming a dye image can be read instead of improving the photosensitive material side. A typical example of this is a technology called cyan dye sound that forms a sound track with cyan coloring dye (reported as "Red LED Reproduction of Cyan Stereo Variable Area Dye Track" at the SMTPE Technical Conference and World Media Expo (1996)). The technical content was disclosed. This technology is a method that can use existing color photographic light-sensitive materials for projection, and can be realized in a developing laboratory with almost no modification to existing facilities. However, this technology requires modification of the sound reader. Actually, the sound scanners attached to projectors on the market are being modified so that they can support cyan dye sound, but in order to replace all silver image soundtracks with this, all projectors must be modified. It is not realistic. In fact, in the current market, there are both a conventional sound reader that uses the infrared region and a sound reader that supports cyan dye sound that uses a cyan color image.

The performance of the conventional sound reader and the cyan dye sound compatible reader is different, and it is necessary to create a soundtrack corresponding to each. Therefore, it is necessary to make a separate production in order to supply cyan dye soundtrack for theaters with cyan die sound equipment and conventional sound tracks for theaters with conventional equipment. It becomes more and more complicated. In order to solve this, a method (high magenta sound track) that changes the color of the conventional sound track and supports both readers has been proposed, but this records sound information as a silver image. Because of this method, the load on the laboratory is the same as before.
US Pat. No. 3,705,208 US Pat. No. 3,705,799 US 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 US Pat. No. 2,266,452 U.S. Pat. No. 3,458,315 US Pat. No. 4,250,251 US Pat. No. 5,030,544 JP-A-63-143546 Japanese Patent Laid-Open No. 11-282106

  Accordingly, an object of the present invention is to overcome the above-mentioned problems and to process a silver halide color photographic light-sensitive material which can be processed by a simplified and shortened exposure / processing step and a processing method thereof, particularly a silver halide color photographic film for movies. A photosensitive material and a processing method thereof are provided. More specifically, the object of the present invention is to firstly eliminate the need for a sound development process dedicated to the formation of a sound track, and from the same sound negative film, it is substantially the same for both a cyan die track compatible projector and a conventional projector. To provide a silver halide color photographic light-sensitive material for movies capable of forming a quality sound track and a processing method thereof. A second object of the present invention is to provide a silver halide color photographic light-sensitive material for movies which can be processed by a simplified processing step and a processing method thereof. Thirdly, an object of the present invention is to provide a silver halide color photographic light-sensitive material for movies capable of reducing the environmental load during processing and a processing method thereof.

As a result of diligent study on solving the above problems, the present inventors have absorbed in the infrared region in order to reproduce substantially the same quality of sound in both the conventional sound reader and the cyan dye sound compatible reader. The present inventors have found that it is important to make the sharpness of the infrared image and cyan dye image forming a conventional sound track having a certain relationship within a specific spatial frequency range, and the present invention has been achieved. Therefore, means for solving the above-described problems are as follows. That is,
<1> At least one layer of 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 transparent support, and non-photosensitive A silver halide color print photosensitive material having at least one photosensitive hydrophilic colloid layer, wherein at least one of the above photosensitive silver halide emulsion layers or any of the above photosensitive silver halide emulsion layers is A photosensitive silver halide emulsion layer having a different color sensitivity range contains a compound capable of forming a dye having an absorption in the infrared region by reacting with an oxidized oxidized developing agent, and the CTF (CI of the formed infrared dye image And the CTF (CC) of the cyan dye image formed from the cyan color-sensitive photosensitive silver halide emulsion layer is represented by the formula 1 in the spatial frequency range of 2 c / mm to 20 c / mm. The silver halide color photographic light-sensitive material to satisfy the engagement.
(Formula 1)
0.95 <CI / CC <1.05
<2> The CTF (CI) of the infrared dye image and the CTF (CC) of the cyan dye image formed from the cyan coloring light-sensitive silver halide emulsion layer are within a spatial frequency range of 2 c / mm to 20 c / mm. The silver halide color photographic light-sensitive material as described in <1>, wherein the relationship of Formula 2 is satisfied.
(Formula 2)
0.98 <CI / CC <1.02
<3> At least one each of 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, A silver halide color print photosensitive material having at least one fourth silver halide emulsion layer having a color sensitivity different from that of the silver emulsion layer and having at least one non-photosensitive hydrophilic colloid layer, 4 contains a compound that suppresses bleaching of developed silver during development processing, forms an image with developed silver after the development processing, and CTF (CI) of the formed silver image; The CTF (CC) of the cyan dye image formed from the cyan color-developing photosensitive silver halide emulsion layer satisfies the relationship of Formula 1 in the spatial frequency range of 2 c / mm to 20 c / mm. The silver halide color photographic light-sensitive material to be butterflies.
(Formula 1)
0.95 <CI / CC <1.05
<4> The CTF (CI) of the silver image and the CTF (CC) of the cyan dye image formed from the cyan coloring light-sensitive silver halide emulsion layer are expressed by the formula 2 in the spatial frequency range of 2 c / mm to 20 c / mm. <3> The silver halide color photographic light-sensitive material according to <3>, which satisfies the following relationship:
(Formula 2)
0.98 <CI / CC <1.02
<5> The silver halide color photographic light-sensitive material according to any one of <1> to <4>, wherein the silver halide color photographic light-sensitive material is for movie projection.
<6> The halogen described in any one of <1> to <5>, wherein the amount of Fe in the silver halide color photographic light-sensitive material is 2 × 10 ⁻⁵ mol / m ² or less. Silver halide color photographic material.
<7> The halogen described in any one of <1> to <5>, wherein the amount of Fe in the silver halide color photographic light-sensitive material is 8 × 10 ⁻⁶ mol / m ² or less. Silver halide color photographic material.
<8> When developing the silver halide color photographic light-sensitive material according to any one of the above items <5> to <7>, re-developing the sound track after exposing the image for forming the sound track A method for processing a silver halide color photographic light-sensitive material for movie projection, characterized by performing color development without performing the steps.

  According to the present invention, a dedicated sound development process is not required for forming a sound track, and the same sound negative film can be used to form a sound track of substantially the same quality in both a cyan die track compatible projector and a conventional projector. A silver halide color photographic light-sensitive material can be provided.

  Hereinafter, the silver halide color photographic light-sensitive material of the present invention will be described in detail.

  In the present invention, CTF (Contrast Transfer Function) is a value serving as an index of image sharpness. Specifically, it is a value measured based on the following method. In other words, a rectangular pattern with a density difference of 0.5 with varying spatial frequency deposited on a glass substrate is brought into close contact with each sample, and exposure is performed with an exposure amount such that the background density is 0.3. At this time, the wavelength (range) of light used for exposure can take any value or range depending on the purpose. Next, a general color development process is performed on the exposed photosensitive material, the density of the obtained rectangular image is precisely measured with a micro densitometer, and the CTF value is calculated from the density difference between the rectangular images at each spatial frequency. . At this time, the wavelength (range) of the light used for the measurement can take any value or range depending on the purpose, and measurement may be performed with so-called white light if necessary.

  As a compound capable of forming a dye having absorption in the infrared region by reacting with the oxidized developer used in the present invention (hereinafter referred to as an infrared coloring coupler), specifically, color development having a maximum absorption wavelength at 750 nm or more. Couplers that form dyes are preferred. A more preferable range of the maximum absorption wavelength is 750 nm to 1200 nm, more preferably 800 nm to 1100 nm, and most preferably 800 nm to 1000 nm. Examples of such couplers include those obtained by adding a long wavelength by adding an electron-withdrawing group to a cyan coupler, and those utilizing an absorption change due to aggregation of the produced dye. Specific examples include U.S. Pat. Nos. 2,266,452, 3,458,315, 4,250,251, 5,030,544, JP-A 63-143546, It is described in Kaihei 11-282106, JP2003-228155A, and the like.

  A compound that suppresses bleaching of developed silver during the development processing used in the present invention (hereinafter referred to as a bleach inhibitor) is a compound that acts on developed silver in the bleaching step in the color development step and inhibits its rehalogenation. It is. The action is desirably developed imagewise, and a compound that reacts with an oxidized form of a color developing agent to release a diffusion-resistant bleach inhibitor is preferable. Specific examples of such compounds include couplers described in U.S. Pat. Nos. 3,705,801, 3,705,799, 4,248,962, and WO97 / 21147, and diffusion resistance. There are hydroquinone, naphthoquinone and the like which release the bleach inhibitor. These have a hydrophobic group bonded to an aromatic nucleus via a thio or seleno group, and react with an oxidized form of a developing agent to release these hydrophobic groups.

  In general, couplers, hydroquinones, and naphthoquinones as described above are generally known thio-substituted development inhibitor releasing compounds such as US Pat. , 632,345, 3,705,799, 3,705,803, couplers of the compounds described in the art, generally known mercapto compounds such as JP-A-2002-162707, The compounds described in JP 2004-54025 A and the like can be preferably used.

  In order to introduce the infrared coloring coupler, bleach inhibitor releasing coupler, hydroquinone, and naphthoquinones into a silver halide photosensitive material, a known dispersion method such as an oil-in-water dispersion method or a latex dispersion method using a high boiling point organic solvent is used. I can do it. In the oil-in-water dispersion method, a cyan coupler and other photographic useful compounds are dissolved in a high-boiling organic solvent, and in a hydrophilic colloid, preferably in an aqueous gelatin solution, together with a dispersant such as a surfactant, an ultrasonic wave, a colloid mill And can be emulsified and dispersed in the form of fine particles by a known apparatus such as a homogenizer, a manton gourin, or a high-speed dissolver. Further, an auxiliary solvent can be further used when the coupler is dissolved. As used herein, the auxiliary solvent is an organic solvent effective at the time of emulsification and dispersion, and is substantially removed from the photosensitive material after the drying process at the time of coating. For example, an acetate of a lower alcohol such as ethyl acetate or butyl acetate, Examples include ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate, methyl carbitol propionate, and cyclohexanone.

  Further, if necessary, an organic solvent that is completely miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide and the like can be used in combination. Moreover, these organic solvents can also be used in combination of 2 or more types. From the viewpoint of improving stability over time during storage in the emulsion dispersion state, suppressing photographic performance changes in the final coating composition mixed with emulsion, and improving stability over time, the emulsion dispersion may be reduced in pressure as necessary. All or part of the auxiliary solvent can be removed by a method such as distillation, washing with noodles or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.04 to 0.50 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.08 to 0.20 μm. It is. The average particle size can be measured using a Coulter submicron particle analyzer model N4 (Coulter Electronics).

  In the oil-in-water dispersion method using a high-boiling organic solvent, the weight ratio of the high-boiling organic solvent to the total cyan coupler weight can be arbitrarily selected, but is preferably 0.1 or more and 10.0 or less, more preferably 0.8. 1 or more and 5.0 or less, most preferably 0.2 or more and 2.0 or less. Moreover, it is also possible to use it without using any high-boiling organic solvent.

  As the high-boiling organic solvent, known high-boiling organic solvents (for example, those described in JP-A-62-215272, JP-A-63-143546, JP-A-2-33144, European Patent 0355660A2, etc.) are preferably used. It is done.

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 print light-sensitive material having a transmissive support, on which the yellow color-developable light-sensitive silver halide emulsion layer and the cyan color are formed. A silver halide color photographic light-sensitive material having at least one layer of each of a photosensitive silver halide emulsion layer and a magenta-color-sensitive photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer. The present invention can be applied to color photographic light-sensitive materials for general use such as color positive film and movie positive film and movie. In particular, it is preferably applied to a color positive photosensitive material for movies.

  In the present invention, the transparent support has at least one yellow color-sensitive silver halide emulsion layer, cyan color-sensitive silver halide emulsion layer, and magenta color-sensitive silver halide emulsion layer, If there is at least one photosensitive hydrophilic colloid layer, there is no particular limitation on the number of layers and the layer order of the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer.

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. The color sensitivity of the photosensitive silver halide emulsion layer containing the infrared coloring coupler of the present invention may be the same as or different from any of the coloring layers. When the color sensitivity of the layer containing the infrared coloring coupler is the same as that of the coloring layer, it is preferable that the layer is the same as the cyan coloring layer. Further, when it is different from the coloring layer, it is preferable to have color sensitivity in the ultraviolet region or infrared region, and it is more preferable to have color sensitivity in the ultraviolet region.
In this case, the CTF (CI) of the formed infrared dye image and the CTF (CC) of the cyan dye image formed from the cyan coloring light-sensitive silver halide emulsion layer have a spatial frequency of 2 c / mm to 20 c / mm. In the range, the relationship of the following formula 1 is satisfied,
(Formula 1) 0.95 <CI / CC <1.05
It is preferable to satisfy the relationship of the following formula 2.
(Formula 2) 0.98 <CI / CC <1.02
If the CI / CC deviates from this range, it becomes difficult to produce a sound negative film that can be recorded with satisfactory sound quality for both the conventional sound track and the cyan die surround track. More specifically, in a cross modulation test, a negative film that can be recorded with a high S / N ratio on one sound track, and the S / N ratio cannot be sufficiently obtained even if the other sound track is recorded.

The silver halide emulsion layer containing the bleaching inhibitor of the present invention needs to be a fourth silver halide emulsion layer having a color sensitivity different from any color forming layer. As long as it is different from the color sensitivity of the color developing layer, it is preferable to have color sensitivity in the ultraviolet region or infrared region, and it is more preferable to have color sensitivity in the ultraviolet region.
In this case, the fourth silver halide emulsion layer contains a compound that suppresses bleaching of developed silver during development processing, forms an image with developed silver after the development processing, and CTF (CI of the formed silver image) And the CTF (CC) of the cyan dye image formed from the cyan color-sensitive photosensitive silver halide emulsion layer satisfies the relationship of the following formula 1 in the spatial frequency range of 2 c / mm to 20 c / mm,
(Formula 1) 0.95 <CI / CC <1.05
It is preferable to satisfy the relationship of the following formula 2.
(Formula 2) 0.98 <CI / CC <1.02
When the CI / CC is out of this range, it becomes difficult to create a sound negative film for the reasons described above.

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 containing the infrared coloring coupler of the present invention, non-photosensitive hydrophilic colloid layer (color mixing preventing layer), magenta color developing photosensitive halogenation Silver emulsion layer, non-photosensitive hydrophilic colloid layer (protective layer).
Further, as another example, a non-photosensitive hydrophilic colloid layer containing a dye solid fine particle dispersion and / or black colloidal silver in order from the support, a yellow color-forming photosensitive silver halide emulsion layer, a non-photosensitive hydrophilic layer. Photosensitive colloid layer (color mixing prevention layer), cyan color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (color mixing preventing layer), infrared coloring coupler of the present invention or bleaching agent-containing photosensitive silver halide An emulsion layer, a non-photosensitive hydrophilic colloid layer (color mixing prevention layer), a magenta color-forming photosensitive silver halide emulsion layer, and a non-photosensitive hydrophilic colloid layer (protective layer).
Further, as another example, 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, and the red of the present invention. Photosensitive silver halide emulsion layer containing external color coupler or bleach inhibitor (also used as color mixing prevention layer), cyan color developing photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (color mixing prevention layer), red of the present invention A photosensitive silver halide emulsion layer containing an external color coupler or a bleaching inhibitor (also used as a color mixing prevention layer), a magenta color development photosensitive silver halide emulsion layer, and a non-photosensitive hydrophilic colloid 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.

  In an area type sound track generally used in sound recording in movies, sound is recorded as a wave image having a constant density. At this time, the frequency of the wave on the image is proportional to the frequency of the sound to be recorded, and the spatial frequency 2 to 20 c / mm is an area of 900 to 9 kHz, which is important for forming a timbre in human speech and various musical instruments. This is a region (overtone region). Therefore, the importance of this area is very high in this audio recording.

  In the present invention, in order to adjust the sharpness of the cyan image and the infrared color image or silver image for the soundtrack to the range of the present invention, it is necessary to adjust the sharpness of one or both of these images. . From the viewpoint of not affecting the image to be appreciated, a method of adjusting the sharpness of an infrared color image or a silver image for a sound track is preferable. As the sharpness adjusting means, known sharpness improving means is used. Specific examples include the use of irradiation prevention dyes and the addition of an antihalation prevention layer. In addition, adjusting the sharpness by adjusting the activity by designing the coupler structure, selecting the dispersing agent, and the like is also an effective means. Further, depending on the type of color sensitivity of the emulsion used in the image forming layer for the sound track, it is also preferable to use an oil-soluble material that remains after development processing within a range that does not affect the viewing angle. For example, as described above, when the color sensitivity of the silver halide emulsion used in the sound track layer is in the ultraviolet region, an infrared coloring coupler, a bleach inhibitor releasing coupler, hydroquinones, naphthoquinones and an oil-soluble ultraviolet absorber are used. Co-emulsified and oil-soluble UV absorbers can be used as an occupation to prevent irradiation. In this case, it is preferable not to diffuse throughout the photosensitive material as in the case of a water-soluble irradiation prevention dye, but to be used only in a layer that requires prevention of irradiation. As such oil-soluble ultraviolet absorbers, benzophenones, benzotriazoles, and triazines are preferably used.

Fe in the silver halide color photographic light-sensitive material of the present invention is mainly brought in by gelatin, intentionally doped emulsion grains, dyes, etc. The Fe content of the present invention is 2 Fe. It is preferably × 10 ⁻⁵ mol / m ² or less (preferably 1 × 10 ⁻⁸ to 2 × 10 ⁻⁵ mol / m ² ), and 8 × 10 ⁻⁶ mol / m ² or less (preferably 1 × 10 ⁻⁸ to 8 × 10 ⁻⁶ mol / m ² ) is more preferable, and 3 × 10 ⁻⁶ mol / m ² or less (preferably 1 × 10 ^{−8 to} 3 × 10 ⁻⁶ mol / m ² ) is most preferable. In the embodiment of the present invention, it is important to define the Fe content (particularly from the viewpoint of storage stability), and it has been confirmed that the effect of this Fe content is significant in the embodiment of the present invention.

  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, hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate), sugars such as sodium alginate and starch derivatives. And a wide range of synthetic polymers such as poly (N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and polyvinyl pyrazole).

  Examples of the silver halide grains used in the present invention 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. As for tabular high silver chloride emulsion grains having a principal plane of (111) or (100), JP-A-6-138619, U.S. Pat. Nos. 4,399,215, 5,061,617, No. 5,320,938, No. 5,264,337, No. 5,292,632, No. 5,314,798, No. 5,413,904, International Publication No. WO94 / 22051, etc. Can be prepared by any method.

  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, and silver halide emulsions having a silver chloride content of 98 mol% or more are preferred as in the emulsion of the present invention.

  The silver halide grains in the photographic emulsion may be those having a regular crystal form such as a cube, octahedron or tetradecahedron, those having a crystal defect such as a twin plane, or a composite form thereof. The grain size of the silver halide may be a fine grain having a grain size of about 0.2 μm or less or a large grain having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Is preferably monodispersed for the purpose of accelerating development, and the coefficient of variation of the grain size of each silver halide grain is preferably 0.3 or less (preferably 0.3 to 0.05), Preferably, it is 0.25 or less (preferably 0.25 to 0.05). The variation coefficient here is represented by a ratio (s / d) between a statistical standard deviation value (s) and an average particle size (d).

  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), pages 863-865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chemie et Physique Photographe, Paul Montel, 1967), "Photoemulsion Chemistry". ”Published by Focal Press (GF Duffin, Photographic Chemistry, Focal Press, 1966),“ Production and Coating of Photoemulsions ”by Zerikman et al., Published by Focal Press (VL Zelikman, et al.,). Making and Coating Photographic Emulsion, Focal Press, 1964). It can be.

  Monodisperse 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 in 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 coated silver amount in the 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 is most preferred. The applied silver amount is 0.01 g / m ² or more, preferably 0.02 g / m ² or more, 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 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 1 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 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.

  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.

  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 of formulas (I), (II) and (III) described on pages 5 to 6 of European Patent EP440,195A2 (particularly I- (1) on page 29);
Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ') on page 5 of European Patent EP310,125A2 (especially (60) and (61) on page 61) and JP-A-6-59411 A compound of formula (I) according to claim 1 (particularly paragraph (0022) of paragraph 0022);
Ligand-releasing compound: a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (particularly, a compound in columns 21 to 41 of column 12);
Leuco dye-releasing compound; U.S. Pat. No. 4,749,641, columns 3-8, compounds 1-6; Fluorescent dye-releasing compound: U.S. Pat. No. 4,774,181 claim 1 COUP-DYE Compounds (especially compounds 1-11 in columns 7-10);
Development accelerator or fogging agent releasing compound: compound represented by formula (1), (2), (3) of column 3 of US Pat. No. 4,656,123 (particularly, (I-22) of column 25) And ExZK-2 on page 75, lines 36-38 of EP 450,637A2; a compound that releases a group that becomes a dye only upon leaving: the formula (I) of claim 1 of US Pat. No. 4,857,447 (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;
Oxidizing agent scavenger of developing agent: Compound (especially I- (1), (2), (6), ( 12) (columns 4-5), 5-10 rows of column 2 of US Pat. No. 4,923,787 (especially compound 1 (column 3); stain inhibitors: pages 4-30 of EP 298321A) 33 lines of formulas (I) to (III), in particular I-47,72, III-1,27 (pages 24 to 48); antifading agent: A-6,7,20,21 of European Patent EP298321A 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69-118), US Pat. No. 5,122,444, columns 25-38 II -1 to III-23, in particular III-10, European Patent E No. 471347A, pages 8-12, I-1 to III-4, especially II-2, US Pat. No. 5,139,931, columns 32 to 40, A-1 to 48, especially A-39,42; Materials for reducing the use of enhancers or color mixing inhibitors: European Patent EP 413124A, pages 5-24, I-1 to II-15, especially I-46;
Formalin scavenger: European patent EP 477932A, pages 24-29 SCV-1 to 28, in particular 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 A compound according to claim 1, in particular 28-29 of column 7;
Preservatives, fungicides: U.S. Pat. No. 4,923,790, columns 3-15, I-1 to III-43, especially II-1,9,10,18, III-25;
Stabilizer, antifoggant: I-1 to (14) of columns 6 to 16 of U.S. Pat. No. 4,923,793, in particular I-1,60, (2), (13), U.S. Pat. 952,483 columns 25-32 compounds 1-65, especially 36;
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-1 to 27 to 29 23, especially V-1, F-I-1 to F-II-43, particularly F-I-11, F-II-8, pp. 33-55 of European Patent EP 445627A, 17-28 of European Patent EP 457153A. III-36 of the page, especially III-1, 3, fine crystal dispersion of Dye-1 to 124 of International Publication WO88 / 04794, compound (I-1) of JP-A 2004-37534 (IV-51) microcrystalline dispersions, especially microcrystalline dispersions obtained by dispersing them by the method described on pages 31 to 35, compounds 1-22 on pages 6-11 of European Patent EP319999A, especially compounds 1, Europe The formulas (1) to (3) of Patent EP519306A Compounds D-1 to 87 (pages 3 to 28), U.S. Pat. No. 4,268,622, compounds 1 to 22 (columns 3 to 10) represented by formula (I), U.S. Pat. , 923, 788, compounds (1) to (31) represented by formula (I) (columns 2 to 9);
UV absorbers: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) of JP-A No. 46-3335, represented by formula (I) of EP 520938A Compounds (3) to (66) (pages 10 to 44) and compounds HBT-1 to HBT-10 (page 14) represented by formula (III), represented by formula (1) of European Patent EP521823 Compounds (1) to (31) (columns 2 to 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. T1 / 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. . The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days), and T1 / 2 is photographic science and engineering by A. Green et al. Photogra. Sci. Eng), Vol. 19, pp. 2,124-129 can be used. T1 / 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.

  The silver halide color photographic light-sensitive material for a movie of the present invention can be processed by a simplified process in which a process related to sound development is removed from a normal development process described below. Specifically, the steps of (4) first fixing bath, (5) washing bath, (9) sound development, and (10) washing in the following steps can be omitted. A normal silver halide color photographic light-sensitive material for movies cannot form a sound track when such a simplified processing is performed, but the silver halide color photographic light-sensitive material for movies of the present invention has a sound track. Can be formed.

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) Stabilization bath

  In the present invention, among the above processing steps, the color development time (step (1) above) is 2 minutes 30 seconds or less (lower limit is preferably 6 seconds or more, more preferably 10 seconds or more, further preferably 20 seconds). Above, most preferably 30 seconds or more), more preferably 2 minutes or less (lower limit is the same as 2 minutes 30 seconds), a preferable result can be obtained.

  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.

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 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 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.

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

[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-
Large emulsion (BO-01)
(Cube, particle size 0.71 μm, particle size distribution 0.09, halogen composition Br / Cl = 3/97)
It was prepared by adding a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 4 × 10 −7 mol / mol silver. To this emulsion, sensitizing dyes (A ′) to (C ′) represented by the structural formula described later were added as follows.
Blue sensitizing dye (A ′); 3.5 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 1.9 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′); 1 .8 × 10 ^-5 mol / mol Ag was further optimally gold-sulfur sensitization using chloroauric acid and triethylthiourea.

Medium size emulsion (BM-01)
(Cube, particle size 0.52 μm, particle size distribution 0.09, halogen composition Br / Cl = 3/97)
It was prepared by adding a silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 6 × 10 ⁻⁷ mol / mol silver. To this emulsion, sensitizing dyes (A ′) to (C ′) represented by the structural formula described later were added as follows.
Blue sensitizing dye (A ′); 6.9 × 10 ⁻⁵ mol / mol silver Blue sensitizing dye (B ′); 2.3 × 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.

Small emulsion (BU-01)
(Cube, particle size 0.31 μm, particle size distribution 0.08, halogen composition Br / Cl = 3/97)
The preparation of BM-01 emulsion was the same as BM-01 except that the grain formation temperature was lowered.
Sensitizing dyes (A ′) to (C ′) represented by the structural formula described below were added as follows.
Blue sensitizing dye (A ′): 8.5 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (B ′): 4.1 × 10 ⁻⁴ mol / mol silver Blue sensitizing dye (C ′): 3 .7 × 10 ⁻⁵ mol / mol silver

-Preparation of red-sensitive silver halide emulsion-
Large size emulsion (RO-01)
(Cube, particle size 0.23 μm, particle size distribution 0.11, halogen composition Br / Cl = 25/75)
It was prepared by adding an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 2 × 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 ′): 4.5 × 10 ⁻⁵ mol / mol silver Red-sensitive sensitizing dye (E ′): 0.2 × 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. 9.0 × 10 ⁻⁴ mol was added per mol of silver.

Medium size emulsion (RM-01)
(Cube, particle size 0.174 μm, particle size distribution 0.12, halogen composition Br / Cl = 25/75)
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 emulsion (RU-01)
(Cube, particle size 0.121 μm, particle size distribution 0.13, halogen composition Br / Cl = 25/75)
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 0.20 μm, particle size distribution 0.11, halogen composition Br / Cl = 3/97)
It was prepared by adding an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide by a control double jet method known in the art. The iridium content was adjusted to 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 ′): 2.8 × 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 0.146 μm, particle size distribution 0.12, halogen composition Br / Cl = 3/97)
Except having changed the particle formation temperature, it was carried out similarly to GO-01, and used the sensitizing dye (G ')-(J') represented by the structural formula mentioned later 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

Small emulsion (GU-01)
(Cube, particle size 0.102 μm, particle size distribution 0.10, halogen composition Br / Cl = 3/97)
Except having changed the particle formation temperature, it was carried out similarly to GO-01, and used the sensitizing dye (G ')-(J') represented by the structural formula mentioned later 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 / mol silver Green sensitive sensitizing dye (J ′): 1.2 × 10 ⁻⁴ mol / mol silver

[Preparation of dye solid fine particle dispersion]
The methanol wet cake of compound (D-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 (D-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 / ^m2 ). The silver halide emulsion represents a coating amount in terms of silver. Further, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener.

[Layer structure of sample 101]
Support / polyethylene terephthalate film

First layer (antihalation 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)
A 3: 1: 6 mixture of silver chlorobromide emulsion BO-01, emulsion BM-01, and emulsion BU-01 (silver molar ratio). 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
・ 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) 0.05
-Solvent (Solv-21) 0.06
・ Solvent (Solv-23) 0.04
-Solvent (Solv-24) 0.002

Fourth layer (red-sensitive silver halide emulsion layer)
A 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-52) 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) 0.04
・ (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)
-1: 3: 6 mixture of silver chlorobromide emulsions GO-01, GM-01, GU-01 (silver molar ratio)
0.49
・ Gelatin 1.55
・ Magenta coupler (ExM ') 0.70
・ (Cpd-49) 0.012
・ (Cpd-51) 0.001
・ (Cpd-52) 0.02
・ Solvent (Solv-21) 0.15

7th layer (protective layer)
・ Gelatin 0.97
・ Acrylic resin (average particle size 2μ) 0.002
・ (Cpd-52) 0.03
・ (Cpd-55) 0.005
・ (CPd-56) 0.08
The compounds used here are shown below.

Sample 101 was produced as described above.

[Preparation of Sample 102]
Sample 102 was prepared by adding a UV photosensitive layer and a color mixing prevention layer between sample 101 and a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer.
[Sixth layer (UV photosensitive layer) coating solution adjustment]
81 g of infrared coloring coupler (ExIR-1) was dissolved in 10 g of solvent (Solv-23), 40 g of solvent (Solv-25), and 100 ml of ethyl acetate, and this solution was 10% containing 40 ml of 10% sodium dodecylbenzenesulfonate. An emulsified dispersion R was prepared by emulsifying and dispersing in 1000 g of an aqueous gelatin solution.
On the other hand, a silver chlorobromide emulsion U1 (cube, grain size 0.174 μm, grain size distribution 0.12, halogen composition Br / Cl = 25/75) was converted into an aqueous silver nitrate solution by a control double jet method known in the art. It was prepared by adding a mixed aqueous solution of sodium chloride and potassium bromide. The iridium content was adjusted to 2 × 10 ⁻⁷ mol / mol silver. The emulsion was optimally chemically ripened by adding a sulfur sensitizer and a gold sensitizer.
The emulsified dispersion R and the silver chlorobromide emulsion U1 were mixed and dissolved, and a necessary amount of gelatin was added to prepare a sixth layer coating solution having the composition described later.

A seventh layer coating solution was prepared in the same manner as the sixth layer coating solution. The same coating liquid as that of the sample 101 was used for the first to fifth layers and the eighth to ninth layers. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as in sample 101. The layer structure and the coating amount of each material are shown below. However, the same layer name as the sample 101 indicates the layer name of the corresponding sample 101. Further, the emulsion coating amount represents a silver conversion coating amount.
[Layer structure of sample 102]
Support, polyethylene terephthalate film (used in sample 101)

First layer (antihalation layer (non-photosensitive hydrophilic colloid layer))
Same as first layer of sample 101

Second layer (blue sensitive silver halide emulsion layer)
Same as second layer of sample 101

Third layer (color mixing prevention layer)
Same as third layer of sample 101

Fourth layer (red-sensitive silver halide emulsion layer)
Same as the fourth layer of sample 101

5th layer (color mixing prevention layer)
Same as the fifth layer of sample 101

Sixth layer (UV-sensitive silver halide emulsion layer)
Silver chlorobromide emulsion U-1 0.13
Gelatin 1.20
IR coupler (ExIR-1) 0.22
・ Solvent (Solv-23) 0.02
-Solvent (Solv-25) 0.11

7th layer (color mixing prevention layer)
・ Gelatin 0.56
・ (Cpd-49) 0.02
・ (Cpd-43) 0.05
・ (Cpd-53) 0.005
-Solvent (Solv-21) 0.06
・ Solvent (Solv-23) 0.04
-Solvent (Solv-24) 0.002

8th layer (green sensitive silver halide emulsion layer)
Same as the sixth layer of sample 101

9th layer (protective layer)
Same as 7th layer of sample 101

[Production of Samples 103 to 105]
Next, samples 103 to 105 were prepared by adding the amount of Cpd-65 shown in Table 2 to the sixth layer of the sample 102.

A sample 106 in which the sixth layer and the eighth layer were replaced in the sample 104 was manufactured.
[Preparation of Sample 107]
A sample 107 in which the third layer and the fifth layer were changed as described below with respect to the sample 101 was produced.
Third layer (ultraviolet-sensitive silver halide emulsion layer and color mixing prevention layer)
-Silver chlorobromide emulsion U-1 0.07
・ Gelatin 1.00
IR coupler (ExIR-1) 0.11
・ (Cpd-49) 0.01
・ (Cpd-43) 0.01
・ (Cpd-61) 0.02
・ (Cpd-62) 0.04
・ (Cpd-65) 0.01
・ Solvent (Solv-23) 0.02
・ Solvent (Solv-25) 0.06

5th layer (UV-sensitive silver halide emulsion layer and color mixing prevention layer)
-Silver chlorobromide emulsion U-1 0.07
・ Gelatin 1.00
IR coupler (ExIR-1) 0.11
・ (Cpd-49) 0.01
・ (Cpd-43) 0.01
・ (Cpd-62) 0.04
・ (Cpd-64) 0.002
・ (Cpd-65) 0.01
・ Solvent (Solv-23) 0.02
・ Solvent (Solv-25) 0.06

[Preparation of sample 108]
A sample 108 was prepared by replacing ExIR-1 in the sixth layer with equimolar ExIR-2 with respect to the sample 104.
[Preparation of sample 109]
A sample 109 was prepared by replacing ExIR-1 in the third layer and the fifth layer with equimolar ExIR-2 with respect to the sample 107.

[Preparation of processing solution]
As a standard processing method for color processing films for movies, the following processing process based on the processing excluding the sound development step was prepared for the ECP-2D process announced by Eastman Kodak Company. Next, for the purpose of creating a development processing state that is in a running equilibrium, an image is developed so that about 30% of the coated silver amount is developed for all the prepared samples, and the exposed samples are colored by the above processing process. Continuous processing (running test) was carried out until the amount of replenisher in the developing bath reached twice the tank capacity.

ECP-2D process (excluding sound development process)
<Process>
Process name Processing temperature (℃) Processing time (seconds) Replenishment amount
(per ml 35mm x 30.48m)
1. Development 39.0 ± 0.1 180 690
2. Stop 27 ± 1 40 770
3. Washing with water 27 ± 3 40 1200
4). First fixing 27 ± 1 40 200
5. Washing with water 27 ± 3 40 1200
6). Bleach 27 ± 1 60 200
7). Washing with water 27 ± 3 40 1200
8). Second fixing 27 ± 1 40 200
9. Washing with water 27 ± 3 60 1200
10. Rinse 27 ± 3 10 400
11. Dry

<Processing liquid formulation>
Tank liquid showing composition per liter Replenisher 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) 0.62ml ―――
Stop Sulfuric acid (7N) 50ml 50ml
Fixing (ammonium thiosulfate (58%) 100ml 170ml
2nd common) Sodium sulfite 2.5g 16.0g
Sodium bisulfite 10.3g 5.8g
Potassium iodide 0.5g 0.7g
Bleaching Proxel GXL 0.07ml 0.10ml
Aqueous ammonia (28%) 54.0 ml 64.0 ml
PDTA 44.8g 51.0g
Ammonium bromide 23.8g 30.7g
Acetic acid (90%) 10.0 ml 14.5 ml
Anhydrous iron nitrate 53.8g 61.2g
Rinse Kodak Stabilizer Additive
0.14ml 0.17ml
Dearcide 702 0.7ml 0.7ml
In the above, CD-2 used in the developing process is a developing agent (4-amino-3-methyl-N, N-diethylaniline), and Proxel GXL used in the bleaching process and Dearcide 702 used in the rinsing process are prevented. It is a glaze.
The treatment using the treatment solution in the running equilibrium state obtained in this manner is designated as treatment A. A process obtained by adding a sound development process to the process A is referred to as a process B.

<Process B process>
<Process>
Process name Processing temperature (℃) Processing time (seconds) Replenishment amount
(per ml 35mm x 30.48m)
1. Development 39.0 ± 0.1 180 690
2. Stop 27 ± 1 40 770
3. Washing with water 27 ± 3 40 1200
4). First fixing 27 ± 1 40 200
5. Washing with water 27 ± 3 40 1200
6). Bleach 27 ± 1 60 200
7). Washing with water 27 ± 3 40 1200
8). Sound development Room temperature 20 Apply 9. Spray water wash 27 ± 3 2 Spray
Ten. Second fixing 27 ± 1 40 200
11． Washing with water 27 ± 3 60 1200
12． Rinse 27 ± 3 10 400
13. Dry

<Processing liquid formulation>
The composition per liter is shown. Since sound development is a smearing process, there is only a tank liquid as a prescription.
Sound development Natrosol 250HR 2.0g
Sodium hydroxide 8.0g
Hexylene glycol 2.0ml
Anhydrous sodium sulfite 50g
Hydroquinone 60g
Ethylenediamine 13ml

[Sample evaluation]
The following three types of exposure filters were prepared for sample exposure.
Filter [1]: A filter for cutting light with a wavelength shorter than 500 nm for producing a normal silver image soundtrack Filter [2]: A filter for cutting light with a wavelength shorter than 650 nm for producing a cyan dye soundtrack Filter [3]: Filters for cutting light with a wavelength of 400 nm to 600 nm for producing an infrared sound track for the photosensitive material of the present embodiment Samples 101 to 109 were evaluated for sharpness, cyan image and infrared image (for sample 101). Silver image). For each sample, a necessary one of the above three types of filters for forming the respective dye image or silver image is selected and exposed through this and an optical wedge for sharpness measurement. The color development process was carried out only in Process B). The CTF for every 2c / mm was measured in the range of 2c / mm to 20c / min for the samples that had been processed. Next, the ratio of the cyan color image to the infrared color image was taken for each spatial frequency, and the value farthest from 1 was taken as the evaluation value.
Next, the following cross modulation test was conducted for the purpose of evaluating the sound characteristics of the sample. First, six processed sound negative films (Eastman Kodak) that recorded two audio signals of 7000 Hz modulated at a constant intensity of 1000 Hz and 400 Hz with a negative density ranging from 2.8 to 3.8 in increments of 0.2. Panchromatec sound negative film No. 2374) was prepared. Next, using each of these negative films and the above filter [2] for each sample, the exposure intensity was adjusted to 2.0, 2.2, and 2.4 using a densitometer Xrite 350 manufactured by Xrite. 3 types of cyan die track samples were prepared. The density was controlled by adjusting the intensity of the light source. The 18 types of cyan die tracks produced by the above processing were reproduced by a cyan dye track sound reader, and the signal intensity ratio was measured by comparing the reproduction signal intensity of 1000 Hz with the signal intensity of the 400 Hz component in the 7000 Hz reproduction signal.
Next, the negative film and the sample 101 having the lowest signal intensity of the 400 Hz component in the negative film and the sample 101 are exposed using the filter [1], and the other sample is exposed using the filter [2]. ) To prepare an infrared soundtrack. At this time, the exposure intensity was adjusted so that the processed sample had an infrared density of 1.0 to 1.5 using a Macbeth densitometer TD-904s to prepare five types of samples. These are played back with a normal sound reader (sound reader attached to the movie projector CINEFORWARD FC-10 manufactured by Fuji Photo Film Co., Ltd.). Compared. If this signal intensity ratio is substantially the same as the signal intensity ratio of the cyan dye track measured earlier, this means that a cyan die track and an infrared sound track having the same characteristics can be produced from the same sound negative.
The results are shown in Table 2.

[Evaluation results]
As seen in samples 103 and 104, the closer the sharpness ratio between the cyan color image and the infrared color image based on the present invention is to 1, the more the negative soundtrack and the infrared soundtrack produced from the same sound negative film. It can be seen that the sound reproduction characteristics are close. Further, as seen in samples 106 to 109, it can be seen that this effect is manifested only by the ratio of CTF representing sharpness, regardless of the type of coupler and the layer configuration. That is, the light-sensitive material according to the present invention can form a sound track that can be used for both a conventional sound reading device and a sound reading device corresponding to a cyan dye sound track from one type of sound negative film.

[Preparation of Sample 201]
A sample 201 in which only the sixth layer was changed as follows with respect to the sample 102 used in Example 1 was manufactured.
[Sixth layer (UV photosensitive layer) coating solution adjustment]
12 g of bleach inhibitor releasing coupler (ExB) was dissolved in 48 g of solvent (Solv-21) and 100 ml of ethyl acetate, and this solution was emulsified and dispersed in 1000 g of 10% aqueous gelatin solution containing 40 ml of 10% sodium dodecylbenzenesulfonate. Dispersion B was prepared.
On the other hand, a silver chlorobromide emulsion U1 (cube, grain size 0.174 μm, grain size distribution 0.12, halogen composition Br / Cl = 25/75) was converted into an aqueous silver nitrate solution by a control double jet method known in the art. It was prepared by adding a mixed aqueous solution of sodium chloride and potassium bromide. The iridium content was adjusted to 2 × 10 ⁻⁷ mol / mol silver. The emulsion was optimally chemically ripened by adding a sulfur sensitizer and a gold sensitizer.
The emulsified dispersion B and the silver chlorobromide emulsion U1 were mixed and dissolved, a necessary amount of gelatin was added, and a sixth layer coating solution was prepared so as to have the composition described later.

  The same coating solution as that of the sample 102 was used for the first to fifth layers and the seventh to ninth layers. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as in sample 102. The coating amount of each material of the sixth layer is shown below. Further, the emulsion coating amount represents a silver conversion coating amount.

Sixth layer (UV-sensitive silver halide emulsion layer)
-Silver chlorobromide emulsion U-1 0.98
Gelatin 2.35
-Bleach inhibitor releasing coupler (ExB) 0.14
・ Solvent (Solv-21) 0.56

[Production of Samples 202 to 205]
Next, samples 202 to 205 were prepared by adding the amount of Cpd-65 shown in Table 3 to the sixth layer of the sample 201.

[Preparation of Sample 206]
A sample 206 in which the sixth layer and the eighth layer were replaced in the sample 203 was manufactured.
[Sample evaluation]
Samples 201 to 206 produced in this manner were evaluated for sound characteristics by the same sharpness and cross modulation test as in Example 1. The development processing of the sample was performed with the processing solution in the running equilibrium state prepared in Example 1. In addition, the process process at the time of silver image sound track preparation was performed by the process A of Example 1 about all the samples. The results are shown in Table 3.

[Evaluation results]
As seen in Samples 202 to 204 and 206, the closer the sharpness ratio between the cyan color image and the silver image based on the present invention is 1, the more negative negative soundtrack and silver image soundtrack made from the same sound negative film. It can be seen that the sound reproduction characteristics are close. Further, as seen in the sample 206, it can be seen that this effect is manifested only by the ratio of CTF representing sharpness, without depending on the layer structure. In addition, when combined with the results of Example 1, the photosensitive material according to the present invention can be applied to a conventional sound reading device from one type of sound negative film regardless of whether an infrared color image or a silver image is used as a conventional sound track. A sound track that can be used also for a sound reading device that supports cyan dye sound track can be formed.

  Addition to the third layer and the fifth layer with respect to the sample 104 manufactured in Example 1 (referred to as Sample 301 in this example) and the sample 203 manufactured in Example 2 (referred to as Sample 302 in this Example) Samples 303 and 304 were prepared by replacing Cpd-62 with Cpd-66. The coating amount of each material of the third layer and the fifth layer of the sample 303 and the sample 304 is shown below.

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-66) 0.04
-Solvent (Solv-21) 0.06
・ Solvent (Solv-23) 0.04
-Solvent (Solv-24) 0.002

5th layer (color mixing prevention layer)
・ Gelatin 0.56
・ (Cpd-49) 0.02
・ (Cpd-43) 0.05
・ (Cpd-53) 0.005
・ (Cpd-66) 0.04
・ (Cpd-64) 0.002
-Solvent (Solv-21) 0.06
・ Solvent (Solv-23) 0.04
-Solvent (Solv-24) 0.002

[Sample evaluation]
The samples 301 to 304 thus produced were aged for 2 weeks under pressure conditions of 35 ° C., 60% relative humidity, and 5 atm. As in Example 1, the sharpness and sound characteristics of the sample before the time test and the sample after the time test were evaluated. Table 4 shows the results of the iron content, the sharpness before and after the aging test, and the sound characteristics. In the table, the signal intensity ratio difference is the absolute value of the difference between the signal intensity ratio (dB) of the cyan dye sound track and the signal intensity ratio of the infrared color image or silver image sound track in the cross modulation test. This shows that the closer to 0, the closer the sound characteristics are, that is, two sound tracks can be created from the same sound negative.

[Evaluation results]
As seen in Samples 301 to 304, among the photosensitive materials based on the present invention, the photosensitive material having a low iron content is more advantageous from the viewpoint of the storage stability of the unexposed photosensitive material.

Claims (8)

The transparent support has at least one layer of 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, and has a non-photosensitive hydrophilic property. A silver halide color print light-sensitive material having at least one colloid layer, wherein at least one of the above light-sensitive silver halide emulsion layers or any of the above light-sensitive silver halide emulsion layers is a color sensitive area. A compound capable of forming a dye having an absorption in the infrared region by reacting with an oxidized developing agent in a different photosensitive silver halide emulsion layer, and a CTF (CI) of the formed infrared dye image; The CTF (CC) of the cyan dye image formed from the cyan color-sensitive photosensitive silver halide emulsion layer satisfies the relationship of Formula 1 within the spatial frequency range of 2 c / mm to 20 c / mm. The silver halide color photographic light-sensitive material characterized by plus.
(Formula 1)
0.95 <CI / CC <1.05 The CTF (CI) of the infrared dye image and the CTF (CC) of the cyan dye image formed from the cyan coloring light-sensitive silver halide emulsion layer are represented by the formula 2 in the spatial frequency range of 2 c / mm to 20 c / mm. 2. The silver halide color photographic material according to claim 1, wherein the relationship is satisfied.
(Formula 2)
0.98 <CI / CC <1.02 At least one layer of 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 transparent support, and the photosensitive silver halide emulsion layer A silver halide color print photosensitive material having at least one fourth silver halide emulsion layer having a color sensitivity different from that of the silver halide color print photosensitive material, and having at least one non-photosensitive hydrophilic colloid layer. The silver halide emulsion layer contains a compound that suppresses bleaching of developed silver during development processing, forms an image with developed silver after the development processing, and the CTF (CI) of the formed silver image, and the cyan color developing photosensitivity The CTF (CC) of a cyan dye image formed from a light-sensitive silver halide emulsion layer satisfies the relationship of Formula 1 in the spatial frequency range of 2 c / mm to 20 c / mm. The silver halide color photographic light-sensitive material that.
(Formula 1)
0.95 <CI / CC <1.05 The CTF (CI) of the silver image and the CTF (CC) of the cyan dye image formed from the cyan coloring light-sensitive silver halide emulsion layer satisfy the relationship of Formula 2 within a spatial frequency range of 2 c / mm to 20 c / mm. 4. The silver halide color photographic light-sensitive material according to claim 3, wherein
(Formula 2)
0.98 <CI / CC <1.02   5. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material is for movie projection. 6. The silver halide according to claim 1, wherein an amount of iron (Fe) in the silver halide color photographic light-sensitive material is 2 × 10 ⁻⁵ mol / m ² or less. Color photographic material. 6. The silver halide according to claim 1, wherein an amount of iron (Fe) in the silver halide color photographic light-sensitive material is 8 × 10 ⁻⁶ mol / m ² or less. Color photographic material.   When developing the silver halide color photographic light-sensitive material according to any one of claims 5 to 7, without performing a re-development step for sound track formation after exposing the image for sound track formation. A method for processing a silver halide color photographic light-sensitive material for movie projection, characterized by performing color development.