JP2001042481A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color photographic sensitive material forming an image whose highlight or white part is less liable to a change in the color (color balance) of stain (coloration) with the lapse of time even by accelerated development and having low dependency on a light source for appreciation. SOLUTION: The silver halide color photographic sensitive material satisfies the conditional expression 0<=A<=2, wherein A is defined by the equation A= (L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2}1/2 (where L*1, a*1 and b*1 show the chromaticity (L*1a*1b*1) of the minimum density part of the sensitive material after development in the CIE1976L*a*b* color system and L*2, a*2 and b*2 show the chromaticity (L*2a*2b*2) of the minimum density part of the sensitive material after development and further post-processing in the color system). The post-processing means washing for 90 sec and subsequent drying.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a silver halide color photographic material having excellent suitability for rapid processing and an image forming method using the same. More specifically, the present invention relates to a silver halide color photographic light-sensitive material capable of providing a color print quickly with a short development processing time and having excellent stability over time of an obtained image, and an image forming method using the same. .

[0002]

2. Description of the Related Art In recent years, in the photographic processing service industry, there has been a demand for high-quality photographic light-sensitive materials which can be processed quickly as part of improving services to users and as a means of improving productivity. In order to respond to this demand, a photographic material containing a high silver chloride emulsion (hereinafter, also referred to as a "high silver chloride print material") is processed in a color development time of 45 seconds, and from the start of the development process to the completion of the drying process. Rapid processing is generally performed in which the total processing time is about 4 minutes (for example, color processing CP-4 manufactured by Fuji Photo Film Co., Ltd.).
5X). However, other color image production methods (eg, electrostatic transfer method, thermal transfer method, ink jet method)
Compared to the rapidity of image production, even with this high-speed processing system for high silver chloride print materials, it is still difficult to say that the processing speed is satisfactory. Ultra-rapid processing at a level of less than one minute is desired.

[0003] To this end, various studies and efforts have been made in the art to improve the suitability for ultra-rapid operation. For example, as a means of improving the suitability for ultra-rapid processing, the amount of the organic material to be applied can be reduced by employing a high-active coupler or a coupler having a large molecular extinction coefficient of the coloring dye, and the amount of the hydrophilic binder applied can be reduced, and the developing speed can be increased. The use of silver halide emulsions is being studied. Also, a method is known in which a silver halide emulsion layer having the slowest developing speed (a layer containing a yellow coupler in a conventional color print material is applied) on a side far from the support to speed up development. For example, JP-A-7-239538, JP-A-7-2
No. 39539.

[0004] However, rapid development processing is often accompanied by a reduction in image quality, and this is a great limitation particularly when achieving ultra-rapid development. The decrease in image quality due to the ultra-rapid speed reduction is due to a decrease in four quality characteristics of image density, gradation, color balance, and whiteness of a highlight portion. The relation between the deterioration of these four quality characteristics and the ultra-rapid processing is related to an increase in fog due to an increase in the developing activity, and a coloring caused by a part of the sensitizing dye in the photosensitive material remaining in the image after the development processing ( (Referred to as residual color), increase in minimum density value (Dmin), poor desilvering, coloring of a white background portion of an image due to a residue in the photosensitive material, deterioration of color balance, and increase of color tone dependency on a viewing light source. The increase in the viewing light source dependence of the color tone often causes a decrease in the whitening effect of the fluorescent whitening agent and the increase in the observation light source dependence. The color tone of the color print is
Since the whitening effect depends on the type of the observation light source because it depends on the radiation intensity in the V region (400 to 350 nm), for example, the external light (natural light) and the ultraviolet light component of some indoor lamps While increasing the whiteness, it causes a lack of yellowness (blueing) in the black portion. Also, depending on the ultraviolet radiation intensity of the observation light source, the color balance between the highlight portion and the middle density portion may be lost. The shorter the processing time, the greater the effect of such a fluorescent whitening agent and observation light source on image quality.

[0005] Vigorous studies in the art have been made on solutions to the defects associated with these ultra-rapid development processes. Methods for suppressing fog and residual color and obtaining a low density Dmin are described in, for example, JP-A-6-39936 and JP-A-6-39936.
Examples of the method described in JP-A-59421 and JP-A-6-202291 and the method for suppressing the increase in image stain over time are described in JP-A-7-140625 and JP-A-5-34147.
No. 0, etc., and methods for reducing residual color include the use of a water-soluble diaminostilbene-based fluorescent brightener and the use of a sensitizing dye having a high hydrophilicity.
36, and the like.

In order to enable ultra-rapid processing without deteriorating image quality, degradation of image quality factors such as image density, gradation, color balance, and whiteness of highlights due to the ultra-rapid processing is performed. Vigorous solution efforts have been made for. However, despite the efforts of the industry, a major problem that still needs to be resolved is that ultra-rapid processing first reduces image stability, specifically the level of highlights. The change with time of the tone and the color balance and the change with time of the color of the white background (color balance) increase, and secondly, the dependency of the image on the viewing light increases. For this reason, even if good image quality can be provided by ultra-rapid processing, there is a problem in that the image quality differs depending on the light source at the place to be watched, and the image quality changes with the passage of time of the image.

As described above, in order to provide services such as providing high quality prints in a short processing time and providing them quickly, it is necessary that the quality of the finished image after development processing be satisfactory. Needless to say. However, at the same time, the quality of the image must be stable over time, and the image quality must be almost the same under ordinary illumination light, but no solution has been found in this regard. It is.

[0008]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems associated with the ultra-rapid processing, thereby providing a color photographic light-sensitive material capable of obtaining a color print satisfactory in image quality and a method for the ultra-rapid processing. It is intended to provide. More specifically, it is an object of the present invention to provide a silver halide color photographic light-sensitive material and a development processing method in which the image quality does not change with time and the viewing light source dependency does not increase even when ultra-rapid processing is performed. That is, ultra-rapid processing is possible, and there is little change over time in the gradation and color balance of the highlight portion of the image obtained, and the color balance (color) of the contamination (coloring) of the white background portion, and depends on the viewing light source. It is an object of the present invention to provide a color photographic light-sensitive material and a developing method which have less property.

[0009]

In view of the fact that the image quality largely depends on the viewer's perception of the color, the present inventor has proposed, as an effective solution to the above problem, the color difference between the white background and the image quality. As a result of intensive research focusing on the relevance to the change over time, the characteristic value A relating to the color difference of the white background portion is determined by the conditional expression [I].
It has been found that the object of the invention can be achieved by using a photographic light-sensitive material and a developing method satisfying the conditions of
The present invention has been reached. That is, the present invention is achieved by the following means.

[0010] 1. A reflective support has at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and at least one red-sensitive silver halide emulsion layer containing a cyan coupler. A silver halide color photographic light-sensitive material, wherein the chromaticity of the unexposed portion of the color photographic light-sensitive material after the development processing satisfies the condition of the following conditional expression [I]. Conditional expression [I] 0 ≦ A ≦ 2 In conditional expression [I], A is defined by the following expression. A = ｛(L ^* ₁ −L ^* ₂ ) ² + (a ^* ₁ −a ^* ₂ ) ² +
(B ^* ₁ −b ^* ₂ ) ²で^1/2 where the values of L ^* ₁ , a ^* ₁ , b ^* ₁ , L ^* ₂ , a ^* ₂ , and b ^* ₂ are respectively the photosensitivity after the development processing. CIE1976 L ^* a ^* b ^* chromaticity (L ^* ₁₎ of the lowest density part of the material in the color space
a ^* ₁ b ^* _1), and represent the said surface color space system of chromaticity of the minimum density part after further subjected to post-processing to the photosensitive material after developing processing _{^{(L * 2 a * 2 b}} * 2) . However, post-processing is 3
A water washing treatment at 5 ° C. ± 5 ° C. for 90 seconds followed by drying. The tristimulus value used for the chromaticity standard is JI
S It is a value determined according to the method described in Z8717.

2. 2. The silver halide color photographic light-sensitive material as described in 1 above, wherein the chromaticity of the unexposed portion satisfies the condition represented by conditional formula [II]. Conditional expression [II] 0.1 ≦ A ≦ 1

3. 3. The silver halide color photographic light-sensitive material as described in 1 or 2, wherein the yellow coupler-containing layer is located farther from the support than the magenta coupler-containing layer and the cyan coupler-containing layer.

4. (1) The total of the amount of the hydrophilic binder in the photographic constituent layer is 6.0 g / m ² or less.
4. The silver halide color photographic light-sensitive material according to any one of items 1 to 3,

5. The method according to any one of claims 1 to 4, wherein the silver halide color photographic light-sensitive material is subjected to imagewise exposure, followed by at least one of color development, desilvering, washing and stabilization, and drying to obtain a color image. Wherein the color development time is from 3 seconds to 14 seconds, and all the processing steps from the start of the color development to the end of the drying are from 10 seconds to 90 seconds. Color image forming method.

6. 6. The color image forming method according to the above item 5, wherein at least one processing step is performed in the presence of at least one compound represented by the following general formula (F).

Embedded imageIn the general formula (F), L¹And L^TwoAre the same but different
May be -OR¹Or -NR^Two(R^Three),
And four substituents L in the general formula (F)¹And L^Two
Is selected from the group of substituents represented by formula (II). here
And R¹And R ^TwoRepresents a hydrogen atom, an alkyl group,
Or an alkyl group having a substituent represented by the following formula (II):
Represents a kill group;^ThreeIs an alkyl group, or the following formula (I
Represents an alkyl group having a substituent of the group represented by I)
You. M is a hydrogen atom, an alkali metal, a tetraalkyl
Represents ammonium or pyridinium. Formula (II) -SO_TwoM, -OSO_TwoM, -COOM, -N (R)_Three
X In the formula (II), X represents a halogen, and R represents an alkyl group.
You. M is a hydrogen atom, an alkali metal, a tetraalkyl
Represents ammonium or pyridinium.

In the above 1, the unexposed portion of the color photographic light-sensitive material after the development processing, that is, the C on the white background portion of the color print
The chromaticity in the IE1976L ^* a ^* b ^* color space (hereinafter abbreviated as CIELAB color space) is further measured by using hot water at 35 ± 5 ° C. immediately after developing the photosensitive material and after developing.
This is based on the finding that the image quality is stable over time when the color difference A of the two satisfies the conditional expression [I], which is obtained after re-watering for two seconds and after subsequent re-drying. In this case, it is sufficient that the color difference satisfies the conditional expression [I] regardless of the chromaticity itself of the white background of the ultra-rapid processed photosensitive material. In other words, even if the chromaticity deviates from the white of D65 (the deviation itself is not preferable in terms of image quality), it is stable if the color difference satisfies the conditional expression [I] over time. is there.

Although the image quality of a color print obtained by ultra-rapid processing of a color photographic material is destabilized with time, the image characteristics include image density, gradation, color balance, and whiteness of a highlight area. It is a feature of the present invention that the problem can be solved by designing the photosensitive material and the developing process so as to satisfy the above simple conditional expression [I] regarding the chromaticity of the white background portion corresponding to the unexposed portion. The same applies to the appreciation light source dependency of the color print, as described in JIS.
If designed to satisfy the conditional expression [I] for a single light source under specific conditions stipulated in the standard and only for a white background portion, it is possible to reduce the viewing light source dependency that appears in various scenes. be able to. A secondary object of the present invention is to provide a new determination method capable of determining the temporal stability of image quality in a short time after the development processing.

The details of the CIE1976L ^* a ^* b ^* color space are described in "Fine Imaging and Color Hard Copy", edited by the Photographic Society of Japan and the Imaging Society of Japan, page 354 (1999).
Year, published by Corona). The three-color stimulus values when using this color space are represented by X,
JIS Z8, which defines a method for measuring tristimulus values of Y and Z coordinates
717 is a value obtained according to the method described in FIG. CIE
The chromaticity in the 1976 L ^* a ^* b ^* color space (hereinafter abbreviated as the CIELAB color space) is measured by setting the reference white chromaticity to CIED65 (6504K), which is the international standard for standard daylight. Therefore, for the measurement for verifying that the above conditional expression [I] is satisfied, any chromaticity measuring device capable of measuring the chromaticity in the CIE1976L ^* a ^* b ^* color space can be used. For example, C-2000 color analyzer manufactured by Hitachi, Ltd. and CIED65 (6504K) as a reference light source
Can be measured.

In order for a silver halide color light-sensitive material for producing a color print to satisfy the above-mentioned conditional expression under ultra-rapid processing, the silver halide emulsion layer containing a yellow coupler is replaced with the silver halide emulsion layer containing a magenta coupler or In contrast to the conventional layer structure disposed on the support side of the cyan coupler-containing silver halide emulsion layer, the yellow coupler-containing silver halide emulsion layer is farther from the support than at least one of the other two emulsion layers. And more desirably, it is more preferably located farther from the support than any of the other two emulsion layers. Similarly, in order to satisfy both the above conditional expressions and ultra-rapid processing, it is advantageous that the amount of the hydrophilic binder in the photographic constituent layer is small, and the total amount of the hydrophilic binder is 6.0 g / m ² or less. Good. Other specific designs of the photosensitive material and the developing process for satisfying the above conditional expressions will be described in the section of the embodiments of the invention.

Thus, by satisfying the above-mentioned conditional expression [I], preferably conditional expression [II], it is possible to avoid a decrease in stability over time even when ultra-rapid processing is performed. By appropriately designing the processing factors, the conventional process of ultra-rapid processing, in which all processing steps after imagewise exposure, color development, desilvering, washing and / or stabilization, and drying, are 10 seconds to 60 seconds. Even if an ultra-rapid wet development process, which has not been performed, is performed, it is possible to avoid a decrease in the temporal stability of the obtained image. In the following description, image storability and image aging stability are used synonymously. In the ultra-rapid processing, the temporal stability of the image is particularly noticeable in the temporal change of the gradation and color balance of the highlight portion and the color balance of the white background portion, so in the following description, as an index of the temporal stability of the image, These changes over time, particularly the change over time of the color balance, are often described, but the effect of the storage stability of the present invention also appears in other storage stability characteristics.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of the present invention will be described below. First, a method for achieving speedup while satisfying conditional expression [I], preferably conditional expression [II] will be described. As described above, the method is to select and combine means for accelerating the development processing so that the above-mentioned conditional expression is expressed from the color paper photosensitive material and the development processing method thereof. May be known emulsion techniques and development processing techniques.

In the present invention, the means for ultra-rapid development include means for promoting development from the processing side such as the temperature and pH of the developing solution, color developing agents and development accelerators, addition of development-promoting materials, and emulsion particles. The development of the photosensitive material, such as the means for accelerating the development of the photosensitive material such as the improvement of chemical sensitization or spectral sensitization, or the improvement of the development processing method, or a combination thereof Good. Further, the individual techniques of the photosensitive material and the development processing method do not need to be new techniques, and any of the existing known techniques may be used or may be used in combination. However, even if ultra-rapid processing is enabled by combining these speeding-up means, if the conditions of the conditional expression [I] found by the present inventors are not satisfied, the temporal stability of the obtained image decreases. ing. No rule has been found as a design guideline for satisfying the condition of the conditional expression [I] in any of the photosensitive material and the development processing. Therefore, for each ultra-rapid processing element, the satisfaction of the condition of the conditional expression [I] is not satisfied. It is necessary to judge the properties by a development test. However, since the development test does not impose any special burden, it is only necessary to first find a combination of the photosensitive material and the development processing capable of ultra-rapid processing, and to verify whether the combination satisfies the conditional expression [I]. Good.

The main techniques which can be used for speeding up the development processing of the present invention are described below. First, as a means for speeding up a photosensitive material, for example, the following techniques can be mentioned. Thinning of Emulsion Layer Thinning of the emulsion layer is effective in increasing the developing speed of the lower layer, in particular, where development progress is likely to be delayed. A typical method is to reduce the amount of binder such as gelatin relative to the amount of silver halide grains and couplers. Finer Emulsion Particles Finer emulsion particles can speed up development, but it is particularly effective to finer blue-sensitive emulsions whose development progress speed is usually slow. For this purpose, the average grain size (equivalent sphere equivalent diameter) of all silver halide emulsion grains contained in the silver halide emulsion layer containing the yellow dye-forming coupler is 0.05 to 1.0 μm.
m, more preferably 0.10 to 0.8 μm, and most preferably 0.15 to 0.6 μm.

Emulsion Grains Tabular Grains If the grains have the same grain size, tabular grains are advantageous because they have a higher development speed. Change of Emulsion Layer Structure A structure in which an emulsion layer having a low development speed is close to the surface, such as a blue-sensitive layer being the uppermost layer, contributes to speeding up. Adjustment of the degree of swelling of the binder The degree of swelling of the photosensitive layer is preferably 1.7 to 8.0, more preferably 2.0 to 5.0, and still more preferably 2.5 to 5.0.
4.0. If the degree of swelling is low, the progress of the development of the lower layer is slowed because the diffusion rate of the chemicals related to the development is decreased. .

Faster swelling speed of binder When the photosensitive layer is rapidly swelled when immersed in a developing solution, the developing speed is increased, and in particular, the progress of development of the lower layer is accelerated. It is effective to use a triazine type hardener. Addition of a development accelerator A method of adding a known development accelerator such as a 1-phenyl-3-pyrazolidone derivative or a bispyridinium salt to an emulsion layer, particularly a method of adding a non-diffusible accelerator to a lower layer is also effective. . Reduction of the amount of coated silver It is advantageous to reduce the amount of silver as much as possible in the range where the color density is at a required level in order to increase the developing speed. To do so, select a coupler with a low silver equivalent as the coupler to be used,
The shape and crystal phase of the silver halide grains are appropriately selected. Use of a combination of high activity or high ε type couplers For example, a pyrroloazole type coupler and a
-Combination of acylaminophenol couplers and the like. The high ε-type coupler refers to a coupler having a large molecular extinction coefficient of the produced dye. (10) Decrease in the amount of sensitizing dye added to the photosensitive material. Loss of the sensitizing dye reduces the sensitivity and lengthens the exposure time during printing, impairing the speed of the entire printing system, but as long as such adverse effects do not occur,
It is effective to reduce the amount of sensitizing dye used. (11) Use of a hydrophilic sensitizing dye. If the sensitizing dye has a hydrophilic group and is of a kind that can be easily washed out, it is advantageous for speeding up the development processing. Among the above-mentioned speeding-up means from the photosensitive material surface, those which make a relatively large contribution to the increase in the development progress speed are:

On the other hand, as a method for speeding up the development processing, the following methods can be mentioned, but the speeding up means applicable to the present invention is not limited to these. Higher Development Temperature The development conditions for color labs on the market are usually about 38 ° C., but can be accelerated by raising the temperature to about 50 ° C. Although it is possible to develop at higher temperatures,
The occurrence of fogging and uneven processing becomes remarkable. Higher concentration of color developing agent If there is room for further increasing the concentration of the color developing agent, it is necessary to extend the washing time, and the concentration can be increased within a range that is not disadvantageous. Use of Highly Active Color Developing Agent As the color developing agent, use of a highly active developing agent such as an N-hydroxypropyl derivative is also effective.

Increasing pH of Developer Solution As long as the supply of the color developing agent is not a factor controlling the speed, it is effective means to increase the pH as long as fogging can be controlled. Use of a development accelerator A development accelerator, such as thiocyanate, which promotes the development of the lower layer is particularly preferable. Combination of Development Inhibitors Many development accelerating means increase the developing speed, but since the accelerating property is greater with respect to the surface layer, the effect is limited in terms of the balance of the developing speed between the layers. Therefore, development can be accelerated by using a known development inhibitor having an effect of suppressing development of the surface layer in combination with the development accelerating means. Specific examples include a method in which 1-phenyl-5-mercaptotetrazole and the like are used in combination with sodium thiocyanate. Use of a hydrophilic, hard-to-dye fluorescent whitening agent By using a brightening agent in the processing solution that is highly hydrophilic and hard to dye, the entire image obtained by development processing, Changes over time are reduced. In addition, the observation light source dependence is significantly reduced. A particularly effective brightening agent is a fluorescent whitening agent represented by the following general formula (F). The fluorescent whitening agent may be added to any bath of a processing solution having a bleaching or fixing ability, such as a bleaching solution, a bleach-fixing solution, a fixing solution, and a stabilizing solution, in addition to a color developing solution.
Among these development processing methods, the particularly advantageous means having a relatively large lower layer development accelerating property are as follows.

[Constitution of photosensitive material] The constitution of a silver halide color photographic light-sensitive material to be combined with development processing conditions in order to satisfy at least conditional formula [I], preferably conditional formula [II] of the present invention will be described in detail below. I do. Gelatin is used as a hydrophilic binder in the silver halide color photographic light-sensitive material satisfying the conditions of the present invention. If necessary, other gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, and sugar derivatives may be used. A hydrophilic colloid such as a cellulose derivative, a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used in combination with gelatin. Gelatin used in the silver halide color photographic light-sensitive material of the present invention may be any of lime-processed gelatin and acid-processed gelatin, and may be gelatin manufactured using any of bovine bone, cowskin, and pigskin as a raw material.
Preferred is lime-processed gelatin made from cow bone and pig skin.

In the present invention, in the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer up to the hydrophilic colloid layer farthest from the support on the side on which the silver halide emulsion layer is provided from the support. The total amount of the hydrophilic binder contained in the composition is 7.4 g / m ² or less, 3.0 g / m ² or more, preferably 6.5 g / m ² or less, 3.5 g / m ² or more, and most preferably 6. 0 g / m ² to 4.0 g / m ²
It is. When the amount of the hydrophilic binder is larger than the range of the present invention, the rapid development of color development processing may be impaired, poor recoloring (incomplete color development due to insufficient oxidizing power), or the rapid processing performance of the washing step may be reduced. The inconvenience becomes apparent and the effect of the present invention cannot be obtained. Above all, poor color reversal changes the image density (increases color) during the lapse of time after processing, thereby impairing the stability of the image.
On the other hand, if the amount of the hydrophilic binder is smaller than the range of the present invention, adverse effects due to insufficient film strength such as pressure cover streaks are likely to occur, which is not preferable.

In the present invention, the silver halide emulsion layer is
Refers to a layer containing a silver halide emulsion in which the silver halide emulsion contained therein can be developed to substantially contribute to dye formation by reaction with a coupler. Therefore, a fine grain emulsion having substantially no sensitivity or a layer containing only colloidal silver and no coupler is not applicable. In the present invention, the silver halide emulsion layer containing the yellow coupler may be provided at a position farther from the support than at least one of the silver halide emulsion layer containing the magenta coupler and the silver halide emulsion layer containing the cyan coupler. More preferably, the silver coupler emulsion layer containing the yellow coupler is coated at a position farthest from the support than the other silver halide emulsion layers, so that color development and desilvering can be accelerated, and sensitizing dyes can be used. It is preferable from the viewpoint of reduction of the residual color.

In the present invention, the oil-soluble component in the photographic component layer is a lipophilic component remaining in the photographic material after processing. Specific examples include high-boiling organic solvents, couplers, color-mixing inhibitors, ultraviolet absorbers, lipophilic additives, lipophilic polymers or polymer latexes, matting agents, and slipping agents. It is added to the layer. Therefore, water-soluble dyes, hardeners, water-soluble additives, silver halide emulsions and the like are not oil-soluble components. In addition, a surfactant is generally used when preparing lipophilic fine particles, but in the present invention, the surfactant is not treated as an oil-soluble component. The total amount of preferred oil-soluble ingredient in the present invention is 4.5 g / m ² or less 2.0 g / m ²
2.5 g / m ² or less, preferably 4.0 g / m ² or less.
m ² or more, most preferably 3.8 g / m ² or less 3.0 g
/ M ² or more.

In the present invention, the ratio of the amount of the oil-soluble component to the amount of the hydrophilic binder in the photographic constituent layer can be arbitrarily set. The preferred ratio in the photographic constituent layers other than the protective layer is 0.05 to 1.50 by weight, more preferably 0.10.
To 1.40, most preferably 0.20 to 1.30. By optimizing the ratio of each layer, the film strength, scratch resistance and curl characteristics can be adjusted.

In the present invention, the thickness of the photographic component layer is preferably from 9.0 μm to 1.0 μm, more preferably 8.0 μm.
m and 2.0 μm or more, and most preferably 7.0 μm or less and 3.5 μm or more. In the present invention, the thickness of the photographic component layer means the thickness of the photographic component layer above the support before processing. Specifically, it can be determined by any of the following methods. First, it is obtained by cutting a silver halide color photographic light-sensitive material perpendicularly to a support and observing the cut surface with an electron microscope. A second method is to calculate the film thickness from the coating amount (g / m ² ) of each component in the photographic constituent layer and the specific gravity. The specific gravity is 1.34 g / ml for typical gelatin used for photographic purposes and 5.59 g / ml for silver chloride particles, and other lipophilic additives can be measured. The film thickness can be calculated.

In the present invention, a cyan coupler which can be preferably used from the viewpoint of rapid processing and color reproducibility is a pyrroloazole type coupler.
And pyrroloazole couplers described in JP-A-324-324 and JP-A-6-347960. More specifically, the above-mentioned JP-A-5
A coupler represented by formula (I) or (II) of JP-313324 or a coupler represented by formula (I) of JP-A-6-347960. Among them, couplers which are excellent in color developability and image fastness and are preferably used are those represented by the following formula [I].

[0035]

Embedded image

[0036] In formula (I) R ^1, R ² each independently represent an alkyl group or an aryl group, R ^3, R
⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group; Z represents a group of nonmetallic atoms necessary to form a saturated ring; R ⁶ represents a substituent; X represents a heterocyclic group , A substituted amino group or an aryl group, and Y represents a hydrogen atom or a group which leaves during the color development process.

The alkyl group represented by R ^{1 to} R ⁵ in the general formula [I] is a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, preferably a linear chain having 1 to 22 carbon atoms, A branched or cyclic alkyl group, particularly preferably having 1 carbon atom
To 8 linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, t-butyl, t-amyl, t-octyl, decyl, dodecyl, cetyl, stearyl, cyclohexyl and 2-ethylhexyl. No. The aryl group represented by R ^{1 to} R ⁵ in the general formula [I] is an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 14 carbon atoms, particularly preferably 6 to 14 carbon atoms. And 10 aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, and 2-phenanthryl.

The group of nonmetallic atoms necessary for forming a saturated ring represented by Z in the general formula [I] is a group of nonmetallic atoms necessary for forming a 5- to 8-membered ring. May be substituted, may be a saturated ring or an unsaturated ring, and the non-metal atoms forming the ring include atoms such as carbon, oxygen, nitrogen and sulfur, and are preferably 6-membered saturated carbon rings. And particularly preferably a cyclohexane ring substituted at the 4-position with an alkyl group having 1 to 24 carbon atoms.

In the general formula [I], the substituent represented by R ⁶ is a halogen atom (for example, chlorine atom, bromine atom),
An aliphatic group (for example, a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl,
t-butyl, tridecyl, t-amyl, t-octyl,
2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4-} 2- [4- (4-
Hydroxyphenylsulfonyl) phenoxy] dodecaneamide {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,
4-di-t-amylphenoxy) propyl), an aryl group (an aryl group having 6 to 36 carbon atoms, for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4- Tetradecanamidophenyl), a heterocyclic group (a heterocyclic group having 1 to 36 carbon atoms, for example,
Imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (C1-C36 straight chain, A branched or cyclic alkoxy group, for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), an aryloxy group (an aryloxy group having 6 to 36 carbon atoms), , Phenoxy, 2-methylphenoxy, 4-
t-butylphenoxy, 3-nitrophenoxy, 3-t
-Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), an acylamino group (an acylamino group having 2 to 36 carbon atoms, for example, acetamido, benzamido, tetradecanamido, 2- (2,4-di-t-)
Amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2-
{4- (4-hydroxyphenylsulfonyl) phenoxy} decaneamide), alkylamino group (having 1 to 3 carbon atoms)
An acylamino group of 6, for example, methylamino,
Butylamino, dodecylamino, diethylamino, methylbutylamino)

Further, an anilino group (an acylamino group having 6 to 36 carbon atoms, such as phenylamino,
Chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-
{2- (3-t-butyl-4-hydroxyphenoxy)
Dodecanamide @ anilino), ureido group (2 to 2 carbon atoms)
36 ureido groups, for example, phenylureido,
Methylureide, N, N-dibutylureido), sulfamoylamino group (sulfamoylamino group having 1 to 36 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-methyl-N-decyl Sulfamoylamino), an alkylthio group (an alkylthio group having 1 to 36 carbon atoms, for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butyl) Phenoxy)
Propylthio), an arylthio group (arylthio group having 6 to 36 carbon atoms, for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecaneamide Phenylthio), an alkoxycarbonylamino group having 2 to 36 carbon atoms (eg, methoxycarbonylamino, tetradecyloxycarbonylamino),
Sulfonamide groups (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide,
p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), a carbamoyl group having 1 to 36 carbon atoms (for example,
N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N-methyl-N-dodecylcarbamoyl, N- {3-
(2,4-di-t-amylphenoxy) propyl} carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N
-(2-dodecyloxyethyl) sulfamoyl, N-
Ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl,
Toluenesulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy groups (eg, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), An azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-
Hydroxy-4-propanoylphenylazo), an acyloxy group (eg, acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg,
Trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-
Succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), aryloxycarbonyl group (eg, phenoxycarbonyl), acyl group (Eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, and an unsubstituted amino group. More preferably, an alkyl group,
An aryl group, more preferably an aryl group in which at least the p-position is substituted with an alkyl group.

X represents a heterocyclic ring, a substituted amino group or an aryl group. The heterocyclic ring is a 5- to 8-membered ring having a nitrogen atom, an oxygen atom or a sulfur atom and having 1 carbon atom.
~ 36 are preferred. More preferably, it is a 5- or 6-membered ring linked by a nitrogen atom, of which a 6-membered ring is particularly preferred. Specific examples include imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine, pyrazolidine, thiazolidine, pyrazoline and the like, preferably morpholine and piperidine, and particularly preferably morpholine. Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the substituents represented by R ⁶ described above, and further include a cyano group, an alkoxy group (eg, methoxy), an alkoxycarbonyl group (eg, ethoxycarbonyl), chloro, a hydroxyl group, a carboxyl group, May be substituted with a group. As the substituted amino group, disubstitution is preferable to monosubstitution. The aryl group has 6 to 3 carbon atoms.
6 are preferred, and a single ring is more preferred. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl,
Methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 2,4-dichlorophenyl and the like can be mentioned.

Y is a hydrogen atom or a compound which is eliminated in the course of color development. For example, as a substituent represented by Y, under an alkaline condition as described in JP-A-61-222844, etc. Groups that can be used and JP-A-56-13373
Substituents that couple off by reaction with a developing agent as described in JP-A No. 4 (1994) -104 are mentioned, and preferably, Y is a hydrogen atom.

The coupler represented by the general formula [I] is a compound represented by R ⁶
Contains a coupler residue represented by the general formula [I] to form a dimer or higher multimer, or R ⁶ contains a polymer chain and forms a homopolymer or a copolymer. It may be formed. The homopolymer or copolymer containing a polymer chain is a typical example of an addition polymer having a coupler residue represented by the general formula [I], homo- or copolymer of an ethylenically unsaturated compound. . In this case, one or more kinds of cyan coloring repeating units having a coupler residue represented by the general formula [I] may be contained in the polymer, and acrylic acid esters, methacrylic acid esters, and maleic acid may be used as copolymer components. It may be a copolymer containing one or more non-color-forming ethylene-type monomers that do not couple with the oxidation product of an aromatic primary amine developer such as esters. Hereinafter, specific examples of the coupler according to the present invention will be shown, but the present invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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The compound represented by the general formula [I] is
Known methods, for example, JP-A-5-255333,
No. -202004, No. 7-48376, No. 8-110
623 can be synthesized.

In the light-sensitive material of the present invention, a cyan coupler represented by the following formula [ADF] is preferably used in combination with a coupler represented by the following formula [I].

[0054]

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In the general formula [ADF], X^fIs hydrogen field
Oxidized product of aromatic or aromatic amine-based developing agent and coupling
Represents a group that leaves upon reaction^f1~ R^f2Are identical to each other
Or may be different, each being a hydrogen atom or substituted
Represents a group. R^f3Represents an alkyl group, an aryl group, an alkyl group
Represents a mino group or an arylamino group. Each of these groups
May be substituted with a substituent.
R in general formula [I] ⁶The groups mentioned in are preferred. R^f1When
R^f2May combine with each other to form a 5- to 6-membered ring. R
^f1~ R^f3At least one of the groups
8 or more. R^f1Is hydrogen atom, alkyl group, halogen
Atoms are preferred and R^f2Is an alkyl group, an acylamino group,
A ureido group is preferred, and X^fIs a halogen atom, a hydrogen atom
Is preferred. Compounds represented by the following general formula [ADF]
The following shows a specific example.

[0056]

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[0057]

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The cyan coupler represented by the general formula [I] is preferably added to the silver halide emulsion layer closest to the support. The content of the cyan coupler represented by the general formula [I] in the light-sensitive material is suitably 1 × 10 ^-3 to 1 mol, preferably 2 × 10 ^-3 mol, per mol of silver halide in the same layer.
It is 10 ^{-3 to} 3 × 10 ^-4 mol. General formula [ADF]
The cyan coupler represented by the formula (I) is preferably added in the same layer as the cyan coupler represented by the general formula [I], and 1 mol% with respect to the cyan coupler represented by the general formula [I].
-100 mol%, more preferably 2-50 mol%, most preferably 2-30 mol%.

Known additives can be used with respect to the cyan coupler represented by the general formula [I] from the viewpoints of hue adjustment, improvement in image fastness, processing stability and the like. For example, JP-A-10-221825, Japanese Patent Application No. 9-2081
6, No. 9-181487, No. 9-181488,
Nos. 9-197992, 9-243371, 9-
No. 282821, No. 10-76596 and No. 10-
The additives described in No. 80368 and the like are preferable.

The cyan coupler represented by the general formula [ADF] can be added to a hydrophilic colloid layer adjacent to a silver halide emulsion layer containing the cyan coupler represented by the general formula [I]. At this time, the hydrophilic colloid layer may or may not contain the silver halide emulsion, but the content is small from the viewpoint of suppressing color reproducibility and color reversal failure affecting image aging stability. Is more preferred. Further, it is preferable to add a polymer described in JP-A-9-171240 or JP-A-9-329861 to the hydrophilic colloid layer from the viewpoint of suppressing poor color reproduction.

The yellow coupler and magenta coupler used in the light-sensitive material of the present invention are not particularly limited, and ordinary couplers can be used. As a specific example,
Those described in each patent listed in Table 1 below are listed. In order to introduce other useful photographic compounds into the silver halide photosensitive material, including the cyan coupler in the present invention,
Known dispersion methods such as an oil-in-water dispersion method and a latex dispersion method using a high-boiling organic solvent described below can be used. In the oil-in-water dispersion method, a cyan coupler and other photographically useful compounds are dissolved in a high-boiling organic solvent,
In a hydrophilic colloid, preferably in an aqueous gelatin solution, together with a dispersant such as a surfactant, it can be emulsified and dispersed in fine particles by a known apparatus such as ultrasonic waves, a colloid mill, a homogenizer, Mentongorin, and a high-speed dissolver. .

In dissolving the coupler and the photographically useful substance, an auxiliary solvent can be further used. The auxiliary solvent referred to here is an organic solvent effective at the time of emulsification and dispersion, which is substantially removed from the photosensitive material after the drying step at the time of coating, for example, ethyl acetate, acetate of lower alcohol such as butyl acetate , Ethyl propionate, se
Examples include c-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate, methyl carbitol propionate and cyclohexane.

Further, if necessary, an organic solvent which is completely miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide and the like can be partially used. These organic solvents can be used in combination of two or more kinds. Further, from the viewpoint of improving the aging stability during storage in the state of an emulsified dispersion, suppressing the change in photographic performance of the final composition for coating mixed with the emulsion, and improving the aging stability, the emulsified dispersion is optionally used. Then, all or a part of the auxiliary solvent can be removed by a method such as distillation under reduced pressure, washing with noodles or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is preferably from 0.04 to 0.50 μm, more preferably from 0.05 to 0.30 μm, and most preferably from 0.08 to 0.20 μm. is there. Average particle size is based on Coulter Submicron Particle Analyzer model
It can be measured using N4 (Coulter Electronics Co., Ltd.) or the like.

From the viewpoint of rapid washing with water, it is preferable to use a small amount of the high boiling organic solvent and other photographically useful compounds, and the total amount of both of them with respect to the coupler is expressed by weight ratio.
Preferably it is 0.05 or more and 8.0 or less, more preferably 0.1 or more and 3.0 or less, and most preferably 0.1 or more and 2.5 or less. In addition, by using a coupler having high activity, it is possible to use a coupler without using a high boiling point organic solvent at all. In the present invention, examples of a high boiling point organic solvent which can be preferably used are described in US Pat. No. 2,322,02.
7 and JP-A-10-221825.

The silver halide grains contained in the photographic emulsion preferably used in the present invention may be cubic, tetrahedral,
Or a regular crystal shape like octahedron,
A shape having an irregular crystal wall such as a sphere or a plate, or a combination of these shapes can be used. A set of parallel planes perpendicular to the thickness direction of the tabular grains is called a main plane. In the present invention, it is preferable to use a photographic emulsion containing tabular grains having a {111} plane as a principal plane or tabular grains having a {100} plane as a principal plane. The tabular silver halide grains used in the light-sensitive material of the present invention will be described in detail.
Regarding the formation of {111} tabular grains, a method using various crystal habit controlling agents is disclosed, but the compounds described in JP-A-2-32 (Compound Examples 1 to 42) are preferable, Crystalline phase controlling agent 1 described in US Pat.
To 29 are particularly preferred. However, the present invention is not limited to these.

{111} tabular grains are obtained by forming two parallel twin planes. Since the formation of the twin plane depends on the temperature, the dispersion medium (gelatin), the halogen concentration, and the like, these appropriate conditions must be set. When a crystal habit controlling agent is present during nucleation, the gelatin concentration is preferably 0.1% to 10%. The chloride concentration is at least 0.01 mol / l, preferably at least 0.03 mol / l. Further, it is disclosed in JP-A-8-184931 that it is preferable not to use a crystal habit controlling agent in forming nuclei in order to monodisperse particles.
When the crystal habit controlling agent is not used at the time of nucleation, the gelatin concentration is 0.03% to 10%, preferably 0.05% to 1.0%.
%. Chloride concentration is 0.001 mol / l to 1
Mol / l, preferably 0.003 mol / l to 0.1 mol / l. Nucleation temperature is 2 ° C-9
Any temperature can be selected up to 0 ° C, but preferably 5 ° C to 80 ° C, and particularly preferably 5 ° C to 40 ° C.

Although nuclei of tabular grains are formed in the first nucleation step, a large number of nuclei other than tabular grains are contained in the reaction vessel immediately after nucleation. Therefore, after nucleation, aging is performed,
A technique for leaving only tabular grains and extinguishing others is required. When ordinary Ostwald ripening is performed, the tabular grain nuclei also dissolve and disappear, so that the tabular grain nuclei decrease and the size of the resulting tabular grains increases. To prevent this, a crystal habit controlling agent is added. In particular, by using phthalated gelatin in combination, the effect of the crystal habit controlling agent can be enhanced and the dissolution of tabular grains can be prevented. The pAg during ripening is particularly important, and is preferably 60 to 130 mV with respect to the silver-silver chloride electrode.

Next, the formed nuclei are grown in the presence of a crystal habit controlling agent by physical ripening and addition of a silver salt and a halide. In this case, the chloride concentration is 5 mol / l or less,
Preferably it is 0.05 to 1 mol / l. The temperature during grain growth can be selected in the range of 10 ° C to 90 ° C.
A range from 0 ° C to 80 ° C is preferred. The total amount of the crystal habit controlling agent is 6 × 10 ⁻⁵ per mol of silver halide in the finished emulsion.
It is preferably at least 3 moles, particularly preferably 3 × 10 ⁻⁴ mole to 6 × 10 ⁻² mole. The phase control agent may be added at any time during the nucleation of silver halide grains, physical ripening, and during grain growth. The {111} plane starts forming after the addition. The crystal habit controlling agent may be added to the reaction vessel in advance, but in the case of forming small-sized tabular grains, it is preferable to add the crystal phase controlling agent to the reaction vessel together with the growth of the grains to increase the concentration.

When the amount of the dispersion medium used at the time of nucleation is insufficient for growth, it is necessary to supplement the amount by addition. Preferably, 10 g / l to 100 g / l of gelatin is present for growth. As the supplemented gelatin, phthalated gelatin or trimellitic acid-added gelatin is preferable. The pH at the time of particle formation is arbitrary, but is preferably in a neutral to acidic range.

Next, the {100} tabular grains will be described. {100} tabular grains are tabular grains having a {100} plane as a main plane. The shape of the main plane is a right-angled parallelogram or a triangular to pentagonal shape in which one corner of the right-angled parallelogram is missing (the missing shape is a side having the corner as a vertex and the corner forming the corner). A right-angled triangular portion formed by
To an octagonal shape. Assuming that the right-angled parallelogram shape supplementing the missing portion is a supplementary quadrilateral, the adjacent side ratio (length of the long side / length of the short side) of the right-angled parallelogram and the supplementary quadrangle is 1 to 6. , Preferably 1-4, more preferably 1
~ 2.

As a method for forming tabular silver halide emulsion grains having {100} major planes, an aqueous silver salt solution and an aqueous halide salt solution are added to a dispersion medium such as an aqueous gelatin solution with stirring and mixed. At this time, for example, JP-A-6-301129 and JP-A-6-347929.
Nos. 9-34045 and 9-96881 disclose that silver iodide or iodide ions or silver bromide or bromide ions are present, and the nuclei are different from silver chloride in the size of the crystal lattice. A method for introducing a crystal defect which causes strain in the crystal and imparts anisotropic growth such as screw dislocation is disclosed. When the screw dislocations are introduced, the formation of two-dimensional nuclei on the surface is not rate-determining under low supersaturation conditions, and crystallization proceeds on this surface, and tabular grains are formed by introducing the screw dislocations. Is done. Here, the low supersaturation condition is preferably 35% or less at the time of critical addition, and more preferably 2% or less.
Indicates 20%. Although it is not determined that the crystal defect is a screw dislocation, it is considered that there is a high possibility that the crystal defect is a screw dislocation because the direction in which the dislocation is introduced or the particles are given anisotropic growth. In order to make tabular grains thinner, it is preferable that the introduced dislocations be retained.
Nos. 122954 and 9-189977.

In Japanese Patent Application Laid-Open No. 6-347928, imidazoles and 3,5-diaminotriazoles are used, and in Japanese Patent Application Laid-Open No. 8-339404, polyvinyl alcohols are used. A method of forming {100} tabular grains by addition is disclosed. However, the present invention is not limited to these.

In the present invention, high silver chloride grains refer to grains having a silver chloride content of 80 mol% or more, preferably 95 mol% or more of silver chloride. The particle of the present invention comprises a core portion and a shell portion surrounding the core portion.
It preferably has a shell structure. It is preferable that 90 mol% or more of the core portion is silver chloride. The core portion may further include two or more portions having different halogen compositions. The shell portion preferably accounts for 50% or less of the total particle volume, particularly preferably 20% or less.
The shell part is preferably silver iodochloride or silver iodobromochloride. The shell part preferably contains 0.5 mol% to 13 mol% of iodine, particularly preferably 1 mol% to 13 mol%. The content of silver iodide in all grains is preferably at most 5 mol%, particularly preferably at most 1 mol%. The silver bromide content is preferably higher in the shell portion than in the core portion. The silver bromide content is preferably at most 20 mol%, particularly preferably at most 5 mol%.

The average particle size (equivalent sphere equivalent diameter) of the silver halide grains used in the light-sensitive material of the present invention is not particularly limited, but is preferably 0.1 μm to 0.8 μm, and particularly preferably 0.1 μm to 0.8 μm. 0.6 μm. The equivalent circle diameter of the tabular grains is preferably 0.2 to 1.0 μm.
Here, the diameter of a silver halide grain refers to the diameter of a circle having an area equal to the grain projected area in an electron micrograph. The thickness is 0.2 μm or less, preferably 0.15 μm or less, particularly preferably 0.12 μm or less. In the present invention, 50% or more of the projected area of all silver halide grains containing a yellow dye-forming coupler has an average aspect ratio (ratio of diameter / thickness) of 2 or more, preferably 5 or more and 20 or less. In general, tabular grains are tabular having two parallel planes. Therefore, the "thickness" in the present invention is represented by the distance between two parallel planes constituting the tabular grains. The grain size distribution of the silver halide grains of the invention may be polydisperse or monodisperse, but more preferably monodisperse. In particular, the coefficient of variation of the equivalent circle diameter of tabular grains occupying 50% or more of the total projected area is preferably 20% or less. Ideally, it is 0%.

If the crystal habit-controlling agent is present on the surface of the grains even after the formation of the grains, it affects the adsorption of the sensitizing dye and the development. Therefore, the crystal habit controlling agent is preferably removed after the formation of the particles. However, when the crystal habit controlling agent is removed, high silver chloride 塩 化 1
It is difficult for 11% tabular grains to maintain {111} planes under normal conditions. Therefore, it is preferable to maintain the particle form by substituting with a photographically useful compound such as a sensitizing dye. This method is described in JP-A-9-80656,
JP-A-9-106026, U.S. Pat. No. 5,221,6
No. 02, No. 5,286,452, No. 5,2
Nos. 98,387, 5,298,388, 5,
176,992.

Although the crystal habit controlling agent is desorbed from the grains by the above method, it is preferable to remove the desorbed crystal habit controlling agent out of the emulsion by washing with water. The washing can be carried out at a temperature at which gelatin usually used as a protective colloid does not solidify. As the water washing method, various known techniques such as a flocculation method and an ultrafiltration method can be used. The washing temperature is preferably 40 ° C. or higher. In addition, the desorption of the crystal habit controlling agent is promoted from the particles at a low pH. Therefore, the pH in the water washing step is preferably low as long as the particles are not excessively aggregated.

The silver halide grains used in the present invention are formed of a metal belonging to Group VIII of the periodic table, ie, a metal ion selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel and iron, or a complex ion thereof. They can be used alone or in combination. Further, a plurality of these metals may be used.

The metal ion-providing compound is added to an aqueous gelatin solution, an aqueous halide solution, an aqueous silver salt solution, or another aqueous solution, which serves as a dispersion medium when silver halide grains are formed, or the metal ions are added in advance. The silver halide grains of the present invention can be incorporated into the silver halide grains of the present invention by, for example, adding them to the silver halide emulsion in the form of fine silver halide grains and dissolving the emulsion. Further, in order to allow the metal ions to be contained in the particles, before forming the particles,
The addition can be performed either immediately after the formation of the particles or immediately after the formation of the particles. The timing of the addition can be changed depending on where and how much metal ions are contained in the particles.

In the silver halide grains used in the present invention, 50 mol% or more, preferably 80 mol% or more, and more preferably 100 mol% of the metal ion donating compound is used. Is preferably localized in the surface layer up to 50% or less. The volume of this surface layer is preferably 30% or less. Localizing metal ions in the surface layer is advantageous for suppressing an increase in internal sensitivity and obtaining high sensitivity. In order to concentrate the metal ion-providing compound in the surface layer of such silver halide grains, for example, after forming the silver halide grains (core) in a portion excluding the surface layer, an aqueous solution for forming the surface layer is formed. It can be carried out by supplying the metal ion providing compound in accordance with the addition of the neutral silver salt solution and the aqueous halide solution.

The silver halide emulsion used in the present invention is
In addition to the Group VIII metal, various polyvalent metal ion impurities can be introduced during the process of emulsion grain formation or physical ripening. The addition weight of these compounds may vary over a wide range depending on the purpose.
0 ^-9 to 10 ^-2 mol is preferred. The silver halide emulsion used in the present invention is usually chemically sensitized. As a chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, U.S. Pat. Nos. 2,448,060 and 3,320,069),
Sensitization with metals such as iridium, platinum, rhodium and palladium (for example, US Pat. Nos. 2,448,060, 2,566,245, 2,566,263, sulfur sensitization using sulfur-containing compounds) Law (eg, U.S. Pat.
22,264)), selenium sensitization using a selenium compound,
Tellurium sensitization using a tellurium compound or reduction sensitization using tin salts, thiourea dioxide, polyamine, etc. (for example, US Pat. Nos. 2,487,850 and 2,518,698)
No. 2,521,925). These sensitization methods can be used alone or in combination.

The silver halide emulsion used in the present invention is
It is preferably subjected to gold sensitization known in the art. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed using a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or salts thereof, gold thiocyanates, and gold thiosulfates can be used. The addition amount of these compounds varies depending on the case, but is not more than 5 mol per mol of silver halide.
× 10 ^{-7 to} 5 × 10 ^-2 mol, preferably 1 × 10 ^-6 to 1
× 10 ^-3 mol. These compounds are added until the chemical sensitization used in the present invention is completed. In the present invention, gold sensitization is carried out by other sensitization methods, for example, sulfur sensitization,
A combination with selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using a compound other than a gold compound is also preferably performed.

The silver halide emulsion used in the present invention contains various compounds or their precursors for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-21.
No. 5,272, pp. 39-72 are preferably used. The emulsion used in the present invention is preferably a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

As the silver halide photographic light-sensitive material used in the present invention, other conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmission type support include transmission films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) and polyesters of NDCA, terephthalic acid and EG. And the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffusion reactive metal surface.

One of the embodiments of the reflective support that can be used in the silver halide color photographic light-sensitive material according to the present invention is that at least one of the water-resistant resin layers between the support and the silver halide emulsion layer has fine voids. A water-resistant resin-coated reflective support, which is a biaxially oriented polyolefin layer having holes, may be used. As a method for forming micropores in the polyolefin, a method in which a substance serving as a nucleus having a low affinity for the polyolefin is added to the polyolefin and then stretched to form pores around the nucleus-forming substance is preferable. The substance serving as a nucleus of the vacancy is called a vacancy inducing substance, and an inorganic pigment or a polymer material can be used, but a polymer material is preferably used. As the polymer material, a polymer that can be melt-mixed with a polymer forming a core matrix and that can form dispersed spherical particles when the suspension is cooled is preferable, and examples thereof include polybutylene terephthalate dispersed in polypropylene. It is preferable to use 5 to 50% by weight of the pore inducing substance based on the matrix polymer of the core. The pore-inducing material particles remaining in the completed sheet core have a diameter of 0.1 to 10 μm and are preferably spherical. The size of the pores depends on the degree of stretching in the vertical and horizontal directions, but is approximately the cross-sectional diameter of the particles that form the pores.

The polyolefin layer having micropores can form a polyolefin layer containing no micropores adjacent to the layer. The polyolefin layer having micropores is opaque and milky white by itself. Whiteness can be improved. In addition, known additives such as pigments, fluorescent whitening agents, and other additives for improving the properties of the polyolefin layer can also be added. In particular, when polypropylene is used, the packing density of titanium oxide or the like can be increased, which is preferable from the viewpoint of improving whiteness. The density of these one or more polyolefin layers is preferably 0.40 to 1.0 g / cc, more preferably 0.50 to 0.70 g / cc.

In a preferred embodiment of the above-mentioned water-resistant resin-coated reflective support, a polypropylene skin layer containing titanium oxide and containing no micropores is provided on both sides of a core layer of polypropylene containing no titanium oxide and having micropores. And a unit having a sandwich structure having the following formula: In this sandwich structure, the thickness of the core layer is preferably 5-150.
μm, more preferably 10 to 70 μm, and the thickness of the skin layer is 1 to 50 μm, more preferably 3 to 20 μm. Further, to improve the adhesion between the hydrophilic photographic component layer and the support,
It is preferable to provide a polyolefin layer having no micropores adjacent to the hydrophilic photographic component layer between the polyolefin layer containing micropores and the hydrophilic photographic component layer. The thickness of the polyolefin layer having no micropores is preferably 0.1 to 5 μm. In a particularly preferred embodiment,
The polyolefin layer having micropores is mainly composed of polypropylene, and the polyolefin having no micropores is preferably polyethylene. Further, it is more preferable that the polyolefin layer having no micropores is subjected to corona discharge treatment.

It is also preferable to provide a biaxially oriented polyolefin layer on the opposite side of the emulsion surface of the support from the viewpoint of increasing the rigidity of the reflection support. In this case, the surface of the polyolefin layer on the back surface is preferably made of matte-finished polyethylene or polypropylene containing silica. Also, JP
As described in No. 1-65024, two or more layers of polypropylene on the back side may be provided, and printing may be performed on the first polyolefin. The thickness of the polyolefin layer on the back surface is preferably 5 to 100 μm, more preferably 10 to 7 μm.
0μ.

The support which can be preferably used in the present invention is a polymer support, a synthetic paper support, a cloth support, a woven polymer fiber support, a cellulose fiber paper support, or a laminate thereof. Particularly preferred is a photographic brand cellulose fiber paper having a base paper pH of 5 to 9 described in JP-A-6-167771. It is also preferable to adjust the thickness and rigidity so as to meet various consumer requirements. For example, for these purposes, a sheet support having a Young's modulus of 2800 MPa to 13000 MPa in the machine direction and a Young's modulus of 1400 MPa to 7000 MPa is provided on both sides of the paper support in the machine direction of 690 MPa to 5520 MPa.
Young's modulus of a and 690MPa-5520MP in longitudinal direction
A laminated support having a biaxially stretched sheet having a Young's modulus of a is prepared with a thickness of about 0.18 mm to 0.28 mm
Flexural stiffness of ~ 250 millinewtons can also be achieved. The preferred embodiments of the support of the present invention described above are described in JP-A-10-333277 and JP-A-10-33327.
No. 8, JP-A-11-52513, JP-A-11-650
No. 24, EP-08880065A1, EP-0880
No. 066A1, US-5,888,681, US-
No. 5,888,714 and British Patent No. 2,325,749.

The above-mentioned reflection type support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizer or antifoggant of silver halide emulsion, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan couplers, magenta or yellow couplers which can be used in combination and their emulsifying and dispersing methods, color image preservability improvers (anti-stain agents and anti-fading agents), dyes (colored layers), gelatin species, layer structure of photosensitive materials and photosensitive materials Regarding the coating pH and the like, those described in the patents in Tables 1 and 2 can be preferably applied to the present invention.

[0091]

[Table 1]

[0092]

[Table 2]

The cyan, magenta and yellow couplers that can be used or used in combination in the present invention include those described in Table 1 above, page 4, upper right column, page 91 to upper left column, page 121 of JP-A-62-215272. 6th line, page 3, upper right column, line 14 to page 18 upper left column last line, page 30 upper right column, line 6 to page 35 lower right column, line 11 of JP-A-2-33144, EP 0355,660A2 Page 4, lines 15 to 2
Line 7, page 30, line 30 to page 28, line 45, page 29 to line 31, page 47, line 23 to page 63, line 50, JP-A-8-122984, JP-A-9-222704 The couplers described in the above items are also useful.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, JP-A-5-333501
No. 9-1, high molecular weight redox compounds described in
No. 40719, U.S. Pat. No. 4,923,787, etc .; phenidone and hydrazine compounds;
No. 9637, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, when increasing the pH of a developer to speed up development, German Patent No. 19618 is used.
No. 786A1, EP 839623 A1, EP 842975 A1, DE 198 06 846
It is also preferable to use the redox compounds described in A1 and French Patent No. 276046A1.

In the present invention, it is preferable to use a compound having a tridian bone nucleus having a high molar extinction coefficient as an ultraviolet absorber. For example, the compounds described in the following patents can be used. JP-A-46-3335, 55
-152776, JP-A-5-197074, and 5-
No. 232630, No. 5-307232, No. 6-211
No. 813, No. 8-53427, No. 8-234364
Nos. 8-239368, 9-31067, 1
Nos. 0-115598, 10-147577, 10
182621, German Patent No. 19739797A,
European Patent No. 711804A and Japanese Patent Publication No. Hei 8-5012
No. 91 and the like.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the photosensitive material, and particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .
The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ^2.
Or less, most preferably 5 mg / m ² or less.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) or a laser beam, in addition to being used in a printing system of a surface exposure method using a so-called negative printer. . A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. For the cathode ray tube used for image exposure, various luminous bodies that emit light in a spectral region are used as necessary. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signals of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high-density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) in which a semiconductor laser or a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design a device which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the photosensitive material of the present invention depends on the scanning used.
It can be set arbitrarily according to the wavelength of the exposure light source.
Solid-state laser using semiconductor laser as excitation light source or
Is obtained by combining a semiconductor laser and a nonlinear optical crystal.
SHG light source can halve laser oscillation wavelength
Therefore, blue light and green light can be obtained. Therefore, photosensitive material
The spectral sensitivity maximum is held in the normal three wavelength ranges of blue, green and red.
It is possible to add. In such scanning exposure
The exposure time is based on the pixel when the pixel density is 400 dpi.
If the size is defined as the exposure time, the preferred exposure
10 for time ^-FourSeconds or less, more preferably 10^-6Seconds
Below.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in Table 2 above. Further, for processing the light-sensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5 upper left column The processing materials and processing methods described in the 17th line to the 20th line on the lower right column on page 18 can be preferably applied. As the preservative used in the developer, the compounds described in the patents listed in Table 2 are preferably used.

Next, the developing method according to the present invention will be described. The developing solution and the developing replenisher contain a color developing agent, and a preferred example is a known aromatic primary amine color developing agent, particularly a p-phenylenediamine derivative. Representative examples are shown below, but are not limited thereto. It is not something to be done.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-Amino-3-methyl-N-ethyl-N- (β-
Hydroxyethyl) aniline 6) 4-amino-3-methyl-N-ethyl-N- (3-
Hydroxypropyl) aniline 7) 4-amino-3-methyl-N-ethyl-N- (4-
Hydroxybutyl) aniline 8) 4-amino-3-methyl-N-ethyl-N- (β-
Methanesulfonamidoethyl) aniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-3methyl-N-ethyl-N- (β-
Methoxyethyl) aniline 11) 4-amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-amino-3-methyl-N- (3-carbamoylpropyl-NN-propyl Aniline 13) 4-Amino-3-methyl-N- (4-carbamoylbutyl-Nn-propylaniline 15) N- (4-Amino-3-methylphenyl) -3-
Hydroxypyrrolidine 16) N- (4-amino-3-methylphenyl) -3-
(Hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-
Pyrrolidine carboxamide

Among the p-phenylenediamine derivatives, particularly preferred are the exemplified compounds 5), 6), 7), 8) and 12), among which the compounds 5) and 8) are preferred. Also, these p-phenylenediamine derivatives are
In the state of solid material, usually sulfate, hydrochloride, sulfite,
It is in the form of a salt such as naphthalenedisulfonic acid and p-toluenesulfonic acid. The concentration of the aromatic primary amine developing agent in the developer or replenisher is preferably 2 to 200 mmol, more preferably 12 to 200 mmol, and still more preferably 12 to 150 mmol per liter of the developer. Yes, the replenisher is designed to have a higher concentration than the developer by the amount consumed by development, and the balance between the amount of replenishment supplied to the developer tank and the amount consumed by the reaction, and the amount lost due to removal to the next tank or overflow. Thus, the concentration of the replenisher is determined so that the concentration in the developing tank is kept constant. Therefore, in the case of the low replenishment process, which is a preferred embodiment of the present invention, the developing agent concentration is set high in order to secure a necessary supply amount with a small replenisher amount.

In the development processing method of the present invention, a small amount of sulfite ions may or may not be substantially contained in the developer depending on the type of the light-sensitive material to be processed. This is because sulfite ions have a remarkable preservative action, but may adversely affect the photographic performance in the color development process depending on the target photosensitive material. Hydroxylamine may or may not be included in the components of the composition depending on the type of the light-sensitive material to be treated. This is because the photographic properties can be affected because the developer itself has a silver developing activity at the same time as the function as a preservative of the developer.

The color developing solution used in the present invention preferably contains an inorganic preservative such as hydroxylamine or sulfite ion or an organic preservative. What is an organic preservative?
It refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being included in a processing solution of a photosensitive material. That is, organic compounds having a function of preventing air oxidation and the like of a color developing agent. Monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused amines, and the like are particularly effective organic preservatives. These are disclosed in JP-A-63-4235, JP-A-63-30845, and JP-A-63-21647.
Nos. 63-44655, 63-53551, 63-43140, 63
-56654, 63-58346, 63-43138, 63-146041
No. 63-44657, No. 63-44656, U.S. Pat.
No. 3, 2,494,903, JP-A-52-143020, JP-B-48
No. -30496 and the like.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
No. 0588, salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat.
An aromatic polyhydroxy compound described in the specification of JP-A No. 4 and the like may be contained as necessary. Among them, alkanolamines are effective in improving the stability over time of a developer or a replenisher itself or a concentrated composition for supplying them as a processing agent.

The alkanolamines particularly effective for improving the stability over time are triisopropanolamine,
Examples thereof include diisopropanolamine, monoisopropanolamine, and diethanolamine, and among them, triisopropanolamine is preferable. In addition, triethanolamines can also be preferably used. The amount of the alkanolamines to be added is 0.01 to 1 mol per liter of the treatment liquid, preferably 0.02 to 0.1 mol.
2 moles.

In addition, a hydroxylamine derivative such as a substituted or unsubstituted dialkylhydroxylamine such as disulfoethylhydroxylamine and diethylhydroxylamine, or an aromatic polyhydroxy compound can be preferably added. Among the above-mentioned organic preservatives, hydroxylamine derivatives are particularly preferred, and details thereof are described in JP-A Nos. 1-97953, 1-186939 and 1-186940.
And No. 1-187557. In particular, it is more preferable to use a hydroxylamine derivative and an amine in combination in view of improving the stability of the color developer and the stability during continuous processing. Examples of other amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines described in JP-A-1-186939. Examples thereof include amines described in JP-A-1-1187557.

A chlorine ion may be added to the developing solution as needed. A color developer (especially a developer for color print materials) usually contains chloride ions of 3.5 × 10 ^{-2 to} 1.5 ×
Although it is often contained at 10 ^-1 mol / l, chloride ions are usually released to a developer as a by-product of development, and therefore, often do not need to be added to a replenisher. The amount of chloride ions in the replenisher is set so that the chloride ion concentration in the developing tank when the running equilibrium composition is reached is at the above-mentioned concentration level. If the chloride ion concentration is more than 1.5 × 10 ^-1 mol / liter, it has the disadvantage of delaying the development, and is unfavorable because the speed and color density are impaired. Also, 3.5 × 10
^If it is less than ^-2 mol / l, it is often not preferable for preventing fog.

Regarding the content of bromine ions, the situation is the same as that of chlorine ions. Color bromide ion in the developing solution is about 1～5X10 ^-3 mol / l in the processing of photographic materials, the processing of the print material is preferably not more than 1.0 × 10 ^-3 mol / liter. The lower limit is a level that does not substantially contain bromine ions other than those released from the photosensitive material. If necessary, bromine ions may be added to the developing replenisher so that the bromine ion concentration falls within this range. When these are included in the developer or the replenisher as necessary, sodium chloride,
Examples thereof include potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, and calcium chloride, and among them, preferred are sodium chloride and potassium chloride. Examples of the bromine ion supply material include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cerium bromide, and thallium bromide. Among them, preferred are potassium bromide and sodium bromide.

When the photosensitive material to be developed is color photographic paper, it is important that the white background of the screen is white. Therefore, stilbene-based fluorescent whitening agents, especially 4,4'-diamino-2,
It is preferable to add a 2'-diaminodisulfostilbene-based fluorescent whitening agent to the color developer. Among them, preferred stilbene-based fluorescent whitening agents are compounds represented by the general formula (F). In the general formula (F), L ¹ and L ² may be the same or different and may be -OR ¹ or -NR.
² (R ³ ) and the four substituents L ¹ and L ² of the general formula (F) are a total of four or more of the formulas (II)
Has the functional groups in the group shown in the following. The four or more functional groups may be the same or different from each other, and L ¹ and L
Either of the ^two may have a functional group, or one may have a functional group. R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an alkyl group having a functional group in the following formula (II), and R ³ has an alkyl group or a functional group in the following formula (II). Represents an alkyl group. [Formula (II)] _{-SO 2 M, -OSO 2 M,} -COOM, -N (R) 3
X In the formula (II), X represents a halogen, and R represents an alkyl group. In the general formulas (F) and (II), M represents a hydrogen atom, an alkali metal, a tetraalkylammonium or a pyridinium.

The general formula (F) will be described in more detail.
I will tell. L¹And L^TwoR in¹, R^TwoAnd R^ThreeBut
When representing a alkyl group, they may be the same or different
A straight-chain or branched alkyl group;
A hydrogen atom of the group may be substituted with another substituent. This
Here, a hydrophilic group is preferable as a group that can be substituted with a hydrogen atom.
No. In particular, in the present invention, R¹, R^TwoOr R^ThreeIs the expression
(II) Al having a strongly hydrophilic functional group selected from the group
It is preferably a kill group. Also, R¹, R ^Two, R^Three
And when R in the formula (II) is an alkyl group, it has 1 to 4 carbon atoms.
Are preferable, and especially 1-2 are preferable. Alky in Table 3
The sulfoethyl group was mentioned as a representative example of the
A propyl group or a sulfobutyl group may be used. Used in the present invention
The compound of the general formula (F) has four substituents L in total of 4
Having at least one functional group represented by the formula (II)
You. Here, as the number of functional groups represented by the formula (II),
Is preferably an even number, and
Is 8 or less, more preferably 6 or less. concrete
Examples of such a structure include diaminos having a substituent shown in Table 3.
And tilbene compounds. For compounds of general formula (F)
For further details, see JP-A-6-329936.
It is described in the gazette.

This stilbene-based fluorescent whitening agent can be added to either a desilvering solution or a photographic material in addition to a color developing solution. When added to a color developer, its preferred concentration is
It is 1 × 10 ^{−4 to} 5 × 10 ⁻² mol / l, more preferably 2 × 10 ^{−4 to} 1 × 10 ⁻² mol / l. The amount of the processing agent composition of the present invention is determined so that the developing solution in use contains the fluorescent whitening agent at this concentration level.

[0115]

[Table 3]

[0116]

[Table 4]

The pH of the color developer or replenisher is 9.5.
To 13.0, more preferably 9.8 to 12.5. In order to maintain this pH, it is preferable to use various buffers. As the buffer, in addition to the above-mentioned potassium carbonate and sodium carbonate, other carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycyl salts, N, N-dimethylglycine salts, Leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane Salts, lysine salts and the like can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent buffering capacity in the high pH range of pH 9.0 or higher, and have an adverse effect on photographic performance (such as fog) even when added to color developers. )
The use of these buffers is particularly preferred because they have the advantage of being inexpensive and inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate,
Potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, o-hydroxybenzoate Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like Can be mentioned. However, the invention is not limited to these compounds. The amount of the above buffer is such that the concentration in the color developing replenisher is from 0.04 to 2.0 mol / l in total of the buffer, especially
It is 0.1 mol / L to 0.4 mol / L.

The color developing solution of the present invention may contain other color developing solution components, for example, various chelating agents which are also agents for preventing precipitation of calcium and magnesium or for improving the stability of the color developing solution. . For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, ethylenediamine N, N-disuccinic acid , N, N-di (carboxylate) -L-aspartic acid, β-alanine disuccinic acid, ethylenediamine
N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2 , 4-Tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-
Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetate, 1,2-dihydroxybenzene-
4,6-disulfonic acid and the like. These chelating agents may be used in combination of two or more as necessary. The amount of these chelating agents may be any amount sufficient to sequester metal ions in the color developer, and the amount is usually 0.1 g to 10 g per liter of the developer or replenisher. It is.

An optional development accelerator can be added to the developer and the replenisher as needed. As a development accelerator,
37-16088, 37-5987, 38-7826, 44-12380
Nos. 45-9019 and U.S. Pat.No. 3,813,247 and the like. Quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, U.S. Pat.
494,903, 3,128,182, 4,230,796, 3,25
No. 3,919, JP-B-41-11431, U.S. Patent No. 2,482,546
Nos. 2,596,926 and 3,582,346, etc.
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431
No. 42-23883 and U.S. Pat.No.3,532,501.
In addition, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as needed.

Further, an optional antifoggant can be added as required. As the antifoggant, the above-mentioned alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used.
Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples. In addition to the surfactant in the present invention, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as necessary.

The processing temperature for color development in the present invention is 3 when the photosensitive material to be developed is a color print material.
It is 0-55 degreeC, Preferably it is 35-55 degreeC, More preferably, it is 38-53 degreeC. Development processing time is 3
５０50 seconds, preferably 3 to 20 seconds, and in particular, the present invention is suitable for extremely rapid development of 3 to 14 seconds. Although it is preferable that the replenishment amount is small, the photosensitive material 1
^{20 to} 600 ml per m ² is suitable, preferably 30 to 120 ml, particularly preferably 15 to 60 ml.
Milliliters. On the other hand, in the case of color development processing of color reversal film or color reversal paper,
The development temperature is 20 to 55, preferably 30 to 55 ° C.
And more preferably 38 to 45 ° C. The development processing time is 10 seconds to 6 minutes. The replenishing amount is preferably smaller, but is suitably 20 to 500 ml, preferably 30 to 200 ml, and particularly preferably 50 to 160 ml per m ^{2 of} the photographic material. The color developing replenisher or developer used in the present invention has been described above.

In practicing the present invention, a desilvering step is carried out after the development step with the color developing solution, and the processing with the bleaching solution and the bleach-fixing solution is performed. When the color printing is a photosensitive material, the processing solution may contain an appropriate compound of a fluorescent whitening agent, preferably a stilbene-based fluorescent whitening agent. ) Is preferably added, and the preferable range of the addition amount is the same as the range of the addition amount to the color developing solution. Particularly preferred compounds include the fluorescent whitening agents described as preferred compounds in the section of the color developing solution.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, known bleaching agents can be used. In particular, organic complex salts of iron (III) (for example, complex salts of aminopolycarboxylic acids) or citric acid or tartaric acid And organic acids such as malic acid, persulfates and hydrogen peroxide. Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids or salts thereof useful for forming an organic complex of iron (III) are listed below. Biodegradable ethylenediaminedisuccinic acid (SS), N- (2-carboxylateethyl) -L-aspartic acid, beta alanine diacetate,
Including methyl iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid,
In addition to glycol ether diamine tetraacetic acid, there can be mentioned compounds represented by the general formula (I) or (II) in European Patent 0789275. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, beta-alanine diacetate,
Ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferable because their iron (III) complex salts have good photographic properties. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid may be used to form a ferric ion complex salt in a solution. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, iron aminopolycarboxylate complexes are preferable, and the amount of addition is 0.01 to 1.0 mol / l, preferably 0.05 to 1.0 mol / l.
0.50 mol / L, more preferably 0.10 to
0.50 mol / l, more preferably 0.15
0.40 mol / liter. The bleaching time is usually 10
Seconds to 6 minutes and 30 seconds, preferably 15 seconds to 2 minutes.

The fixing agents used in the bleach-fixing solution or the fixing solution include known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide dissolving agents such as thioureas;
These can be used alone or in combination of two or more. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution used in the present invention is preferably from 3 to 8, more preferably from 4 to 7. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco-formation of the cyan dye are promoted. Conversely p
If H is higher than this, desilvering will be delayed and stain will easily occur. The pH range of the bleaching solution used in the present invention is 8 or less, preferably 2 to 7, and particularly preferably 2 to 6.
If the pH is lower than this, the deterioration of the solution and the leuco conversion of the cyan dye are promoted, and if the pH is higher than this, desilvering is delayed,
Stain is likely to occur. To adjust the pH,
If necessary, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added.

The bleach-fixing solution may contain other various types of fluorescent whitening agents, defoamers or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, Sulfite ion releasing compounds such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and arylsulfinic acids such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid It is preferable to contain the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.

As a preservative, in addition to the above, ascorbic acid, carbonyl bisulfite adduct, or carbonyl compound may be added. Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary. The bleach-fix processing according to the present invention requires a processing time of 5
２４０240 seconds, preferably 10-60 seconds. The processing temperature is from 25C to 60C, preferably from 30C to 50C.
The replenishing rate is ²⁰ ml to 250 per m ² of the photosensitive material.
ml, preferably 30 ml to 100 ml, particularly preferably 15 ml to 60 ml.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed. The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions.
Among them, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture).
and Television Engineers) Vol. 64, pp. 248-253 (1955
May issue). Usually, the number of stages in the multistage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Occurs. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively.
Further, chlorinated fungicides such as isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-26761. Benzotriazole, copper ion, and others described in the official gazette.
1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) Can be used.

Also, aldehydes such as formaldehyde, acetaldehyde and pyruvaldehyde which inactivate the remaining magenta coupler to prevent color fading and stain formation, methylol compounds described in US Pat. No. 4,786,583 and hexamethylentetramine Hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, seized patent publication 504609.
And azolylmethylamines described in JP-A Nos. 519190 and 519190 are added.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Continue with the above washing process or
Alternatively, the treatment can be performed directly with the stabilizing solution without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound represented by formalin, a buffering agent for adjusting a membrane pH suitable for stabilizing a dye, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly performed without going through a washing step, a known method described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like can be used. Can be used. In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment. The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C. Drying is performed following the washing and / or stabilizing step. From the viewpoint of reducing the amount of water carried into the image film, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a means of improvement from the dryer side, as a matter of course, it is possible to speed up the drying by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in Japanese Patent Application Laid-Open No. 3-157650, drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material and removing the exhaust air.

The processing method of the present invention is performed using an automatic developing machine. The automatic developing machine preferably used in the present invention is described below. In the present invention, it is preferable that the linear velocity of conveyance of the automatic developing machine is 5000 mm / min or less. It is more preferably from 200 mm / min to 4500 mm / min, particularly preferably from 500 mm / min to 3000 mm / min. In the treatment tank and the replenisher tank of the treatment liquid according to the present invention, the area (opening area) where the liquid comes into contact with air is preferably as small as possible. For example, assuming a value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank, the opening ratio is preferably 0.01 (cm ⁻¹ ) or less, more preferably 0.005 or less. And most preferably 0.001 or less.

In order to reduce the area in contact with air, it is preferable to provide a solid or liquid air non-contact means floating on the liquid surface in the processing tank and the replenishing tank. Specifically, it is preferable to float a float made of plastic or the like on the liquid surface, or to cover with a liquid that does not mix with the processing liquid and does not cause a chemical reaction. Preferred examples of the liquid include liquid paraffin and liquid saturated hydrocarbon.

In the present invention, in order to perform the processing quickly, the shorter the air time, that is, the crossover time, when the photosensitive material moves between the respective processing solutions, the better, preferably 10 seconds or less, more preferably 7 seconds or less. The time is not more than seconds, more preferably not more than 5 seconds. In order to achieve the above-mentioned short-time crossover, the present invention preferably employs a cine-type automatic developing machine, and particularly preferably employs a leader transport system. Such a system is developed by Fuji Photo Film Co., Ltd. automatic developing machine FP-56.
0B. Japanese Patent Application Laid-Open Nos. Sho 60-191257 and 60-19
No. 1258 and No. 60-191259 are preferred. Particularly, as a transport mechanism, Japanese Patent Application No. Hei.
-265794, 1-266915, 1-26
It is preferable to adopt each system described in No. 6916.
Further, in order to shorten the crossover time and prevent the treatment liquid from being mixed, the crossover rack preferably has a mixing prevention plate described in Japanese Patent Application No. 1-265975.

It is preferable to perform so-called evaporation correction, in which water corresponding to the amount of evaporation of the processing liquid is supplied to each processing liquid in the present invention. Particularly, it is preferable in a color developing solution, a bleaching solution or a bleach-fixing solution. A specific method for replenishing such water is not particularly limited. Among them, a monitor water tank different from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed. The amount of water in the inside of the bleaching tank is calculated, the amount of water in the bleaching tank is calculated from the amount of evaporation of the water, and the water is replenished to the bleaching tank in proportion to the amount of evaporation, as disclosed in Japanese Patent Application No. 2-46743. 2-4
No. 7777, No. 2-47778, No. 2-47779
And an evaporation correction method using a liquid level sensor and an overflow sensor described in JP-A-2-117972. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation.
As described in JP-A-4-49925, page 1, right column, line 26 to page 3, left column, line 28, and Japanese Patent Application No. 2-103894, the operation time, stop time and temperature control time of the automatic developing machine are described. The amount of water calculated by a coefficient determined in advance based on the information is added.

It is also necessary to devise measures to reduce the amount of evaporation, and it is necessary to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferable aperture ratio of the color developing solution is as described above, but it is preferable to similarly reduce the opening area in other processing solutions. As means for reducing the amount of evaporation, it is particularly preferable to "maintain the humidity of the upper space of the processing tank at 80% RH or more" described in JP-A-6-110171, and the evaporation prevention rack shown in FIGS. It is particularly preferable to have a roller automatic cleaning mechanism. Exhaust fan is mounted in order to prevent dew condensation at the temperature control, preferred emissions, per minute 0.1 m ³ to 1 m ^3, a particularly preferred displacement volume,
It is a 0.2m ³ ~0.4m ^3. The drying conditions of the photosensitive material also affect the evaporation of the processing liquid. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 6 m ³ through 10m ³ preferred. The thermostat for preventing heating of the ceramic hot air heater is preferably operated by heat transfer,
It is preferable that the mounting position is mounted on the leeward or upwind side through the heat radiation fins or the heat transfer portion. The drying temperature is preferably adjusted by the water content of the photosensitive material to be processed,
The optimum temperature is 45 to 55 ° C for a 35 mm wide film and 55 to 65 ° C for a brownie film. A replenishing pump is used for replenishing the processing solution, and a bellows type replenishing pump is preferable. Further, as a method of improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishment nozzle in order to prevent backflow when the pump is stopped. A preferred inner diameter is 1 to 8 mm, and a particularly preferred inner diameter is 2 to 5 mm.

Various parts materials are used in the automatic developing machine. Preferred materials are described below. The tank material such as the treatment tank and the temperature control tank is preferably a modified PPO (modified polyphenylene oxide) or a modified PPE (modified polyphenylene ether) resin. The modified PPO includes "Noryl" manufactured by Nippon GE Plastics Co., Ltd., and the modified PPE includes "Zylon" manufactured by Asahi Kasei Kogyo, "Iupiece" manufactured by Mitsubishi Gas Chemical, and the like. In addition, these materials are suitable for parts that may come into contact with the processing liquid, such as processing racks and crossovers.

The material of the roller in the processing section is preferably a resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), or TPX (polymethylpentene). These materials can also be used for other treatment liquid contact parts. In addition, PE resin is also preferable for the material of the replenishment tank formed by blowing. Materials for processing parts, gears, sprockets, bearings, etc. include PA (polyamide), PBT (polybutylene terephthalate), UH
Resins such as MPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), and LCP (fully aromatic polyester resin, liquid crystal polymer) are suitable. The PA resin is a polyamide resin such as 66 nylon, 12 nylon, 6 nylon, and the like, and a resin containing glass fiber, carbon fiber, or the like is strong against swelling due to the treatment liquid and can be used.

A high-molecular weight product such as MC nylon or a compression-formed product can be used without fiber reinforcement. Unreinforced products are suitable for UHMPE resin, such as Mitsui Petrochemical Co., Ltd.'s "Lybuma", "Hi-Zex Million" Sakushin Kogyo Co., Ltd. "New Light", Asahi Kasei Kogyo Co., Ltd. "Sun Fine", etc. Are suitable. The molecular weight is preferably 1,000,000 or more, more preferably 100
10,000 to 5 million. The PPS resin is preferably glass fiber or carbon fiber reinforced. The LCP resin includes “Victrex” by ICI Japan Co., Ltd., “Econol” by Sumitomo Chemical Co., Ltd., “Zyder” by Nippon Oil Co., Ltd., and “Vectra” by Polyplastics Co., Ltd. Particularly, as the material of the conveyor belt, an ultra-high-strength polyethylene fiber or polyvinylidene fluoride resin described in Japanese Patent Application No. 2-276886 is preferable. As a soft material such as a squeeze roller,
A foamed vinyl chloride resin, a foamed silicone resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd. As a rubber material such as a pipe joint, an agitation jet pipe joint, or a sealing material, EPDM rubber, silicon rubber, viton rubber, or the like is preferable.

The drying time is preferably from 30 seconds to 2 minutes, more preferably from 40 seconds to 80 seconds. As described above, the continuous processing by the replenishment method has been mainly described. In the present invention, the processing is performed without performing the replenishment with a certain amount of the processing liquid, and then the whole or a part of the processing liquid is replaced with a new liquid and the processing is performed again. Can be preferably used.

The treating agent applicable to the present invention may be supplied as a concentrate having a single or plural part constitution, or may be supplied in the form of powder, tablet, granule, paste or the like.
Also, it may be supplied in the state of use liquid, concentrated solution, powder, tablet,
Any combination of granules, pastes, and use solutions may be used.

In the case of a single concentrated solution, it is diluted and used as a replenisher. In this case, it is preferable to automatically dilute with water in the replenisher tank by setting the concentrate in the developing machine. As this water, it is preferable to use water from a washing water replenishing tank. Alternatively, the processing solution may be directly replenished with the concentrated liquid, and water suitable for the dilution ratio may be directly refilled into the processing solution. It is particularly preferable for a compact developing machine having no replenishing tank.

The same applies to the concentrated solution having a plurality of parts. It is preferable that the concentrated solution is set in the developing machine and automatically diluted with water in the replenisher tank. As this water, it is preferable to use water from a washing water replenishing tank. Further, the processing tank may be directly replenished for each part, and water corresponding to the dilution rate may be directly replenished to the processing tank.

Similarly, in the case of a powder, tablet, granule, or paste-like treatment agent, it is also preferable to add the drug directly to the treatment tank and to add water suitable for the dilution ratio to the treatment tank. It is also preferable that the solution is automatically dissolved and diluted in a replenishing tank and used as a replenishing solution.

As the material of the refill cartridge used in the present invention, any material such as paper, plastic and metal can be used, but a plastic material having an oxygen permeability coefficient of 50 ml / m ² · atm · day or less is particularly preferable. . The oxygen permeability coefficient is “O ₂ permeation of plastic container, modern packing” (O ₂ permeation of plastic container, Modern
Packing; NJCalyan, 1968), December 143-1
It can be measured by the method described on page 45. Examples of preferred plastic materials include vinylidene chloride (PVDC), nylon (NY), polyethylene (PE), polypropylene (PP), polyester (PES), ethylene-vinyl acetate copolymer (EVA), and ethylene-vinyl. Alcohol copolymer (EVAL), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyethylene terephthalate (PE
T) and the like. In the present invention, in order to reduce oxygen permeability, PVDC, NY, PE, EVA, EVAL and PE
The use of T is preferred.

These materials may be used singly and may be used after shaping, or a method in which a film is formed and a plurality of kinds of films are bonded and used (so-called composite film) may be used. Further, as the shape of the container, various shapes such as a bottle type, a cubic type, and a pillow type can be used, but the present invention provides a cubic type which is flexible, easy to handle, and can be reduced in volume after use. Structures similar to are particularly preferred.

When used as a composite film, the following structures are particularly preferred, but the invention is not limited thereto. PE / EVAL / PE, PE / aluminum foil / PE, NY / PE / NY, NY / PE / EVA
L, PE / NY / PE / WVAL / PE, PE / NY /
PE / PE / PE / NY / PE, PE / SiO ₂ film / P
E, PE / PVDC / PE, PE / NY / aluminum foil / PE, PE / PP / aluminum foil / PE, NY /
PE / PVDC / NY, NY / EVAL / PE / EVA
L / NY, NY / PE / EVAL / NY, NY / PE /
PVDC / NY / EVAL / PE, PP / EVAL / P
E, PP / EVAL / PP, NY / EVAL / PE, N
Y / aluminum foil / PE, paper / aluminum foil / P
E, paper / PE / aluminum foil / PE, PE / PVDC
/ NY / PE, NY / PE / aluminum foil / PE, P
ET / EVAL / PE, PET / aluminum foil / P
E, PET / aluminum foil / PET / PE,

The thickness of the composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns. The content of the completed container is 100 ml to 20 liter, preferably 500 ml to
It is about 10 liters. The above container (cartridge)
May have a cardboard or plastic outer box,
It may be formed integrally with the outer box. The cartridge of the present invention can be filled with various processing liquids. For example, a color developer, a black-and-white developer, a bleaching solution, an adjusting solution, a reversing solution, a fixing solution, a bleach-fixing solution, a stabilizer and the like can be mentioned. It is preferred to use a developer, a fixer and a bleach-fixer.

Conventional processing liquid containers include high-density polyethylene (HDPE) and polyvinyl chloride resin (PVC).
C), a rigid container using a one-layer material such as polyethylene terephthalate (PET) or a multilayer material such as nylon / polyethylene (NY / PE) can be used. Also, after the contents are discharged and emptied, the volume of the container can be reduced, that is, a flexible liquid container that can easily reduce the required space can be used. In the present invention, it is preferable to use a container having the above flexibility.
As a specific example of the flexible container, there is provided a liquid container in which a hard mouth projecting upward from a flexible container body is opened and closed by a lid member engaged with the flexible body, and the container body and the mouth Is integrally formed and has a bellows portion in at least a part of the height of the container body (Japanese Patent Application Laid-Open No.
FIG. 1 and FIG. 2) described in Japanese Patent No. 5670 can be mentioned.

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EXAMPLES The present invention will be described below with reference to examples, but embodiments of the present invention are not limited thereto.
Further, in the description of each of the following examples, the blue-sensitive emulsion layer, the green-sensitive emulsion layer, the red-sensitive emulsion layer, a yellow coupler-containing layer, a magenta coupler-containing layer, a cyan coupler-containing layer, or After the development, they are called a yellow coloring layer, a magenta coloring layer, and a cyan coloring layer. They may be abbreviated as BL, GL, and RL.

Example 1 (1) Preparation of Photosensitive Material Sample After a corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was used. And a first to seventh photographic constituent layers are sequentially coated to obtain a sample 1 of a silver halide color photographic light-sensitive material having the following layer structure.
01 was produced. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (ExC-1), 250 g of color image stabilizer (Cpd-1), 1 color image stabilizer (Cpd-9)
0 g, color image stabilizer (Cpd-10) 10 g, color image stabilizer (Cpd-12) 20 g, ultraviolet absorber (UV-1) 1
4 g, UV absorber (UV-2) 50 g, UV absorber (UV-3) 40 g and UV absorber (UV-4) 6
0 g was dissolved in 230 g of a solvent (Solv-6) and 350 ml of ethyl acetate, and this solution was emulsified and dispersed in 6500 g of a 10% aqueous gelatin solution containing 200 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, a 1: 4 mixture (silver molar ratio) of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C having an average grain size of 0.51 μm) and a coefficient of variation of grain size distribution Are 0.09 and 0.11, respectively, and each of the emulsions of each size is composed of grains in which 0.5 mol% of silver bromide is locally contained in a part of the surface of a grain based on silver chloride). Prepared. In this emulsion, the following red-sensitive sensitizing dyes G and H were used in an amount of 6.0 × 10 ⁻⁵ mol per mol of silver per mol of silver.
^Are added in an amount of 9.0 × 10 ⁻⁵ mol. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer, except that the compositions were changed to have the compositions described below. Ab-1 was added to each layer.
Ab-2, Ab-3 and Ab-4 each had a total amount of 1
^{5.0mg / m 2, 60.0mg / m} 2, 5.0mg / m 2 and 1
0.0 mg / m ² was added.

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

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(Sensitizing dyes A and C were each added in an amount of 0.42 × 10 ^-4 mol per mol of silver halide.
Sensitizing dye B was 3.4 × 10 ^-4 per mol of silver halide.
Mol was added. Green sensitive emulsion layer

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 ^-4 mol for a large-sized emulsion, 3.6 × 10 ^-4 mol for a small-sized emulsion, and sensitizing dye E
Per mol of silver halide, 4.0 × 10 ^-5 mol for large-size emulsion and 7.0 × ^10-5 mol for small-size emulsion.
10 ^-5 mol, and 2.0 x 10 ^-4 mol of sensitizing dye F per mol of silver halide per mol of silver halide, and 2.8 x 10 ^-4 mol of small sized emulsion per mol of silver halide. Was added. ) Red-sensitive emulsion layer

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(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0^-Five10.7x each for mole and small size emulsions
10 ^-FiveMole was added. Further, the following compound I was added to a red-sensitive emulsion layer by using silver halide.
3.0 × 10 per mole^-3Mole was added. )

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Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × 10 5 per mole of silver halide. ^-4 mol, 1.0 × 10 ^-3
Mol and 5.9 × 10 ^-4 mol. Further, each of the second, fourth, sixth and seventh layers also has 0.2
mg / m ² , 0.2 mg / m ² , 0.6 mg / m ² , and 0.1 mg / m ² . Further, 4-hydroxy-6-methyl-1,3,3 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol of 3a, 7-tetrazaindene were added per mol of silver halide.
In the red-sensitive emulsion layer, a copolymer of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200,000 to 40,000) was used.
0) was added at 0.05 g / m ² . Further, the second layer, respectively 6 mg / m ² disodium catechol-3,5-disulfonate in the fourth layer and the sixth ^{layer, 6mg / m 2, 18mg /} m 2
Was added so that To prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses indicates the coating amount). As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ; content: 16% by weight, ZnO: content: 4% by weight) and a fluorescent whitening agent (4,4′-bis (benzoxa) 8/2 mixture of zolyl) stilbene and 4,4'-bis (5-methylbenzoxazolyl) stilbene: 0.05% by weight), including bluish dye (ultramarine)

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion A (cubic, average grain size 0.74 μm, variation coefficient of grain size distribution 0.08, silver bromide 0.3 mol% Which is locally contained in a part of the surface of a grain based on silver chloride) 0.26 gelatin 1.35 yellow coupler (ExY) 0.62 color image stabilizer (Cpd-1) 0.08 color Image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-sized emulsion B having an average grain size of 0.45 μm and small-sized emulsion B having a 0.35 μm size (silver mole) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer ( Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 colors Image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large emulsion C having an average grain size of 0.50 μm and small emulsion C of 0.41 μm (silver mole) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-1) 0.30 Ultraviolet absorber (UV-1) 0.14 Ultraviolet absorber (UV-2) 0.05 Ultraviolet absorber (UV-3) 0.04 UV absorber (UV-4) 0.06 Color image stabilizer (Cpd-1) 0.25 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer Agent (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.19 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 Ultraviolet absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25

Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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Next, based on the sample 101, the following 1) to
Samples 102 to 110 were prepared by changing the factors of the photosensitive material shown in 3). 1) Change of Blue-Sensitive Silver Halide Emulsion Sample 103 The amount of sensitizing dyes A, B and C was reduced by 25% with respect to silver chlorobromide emulsion A of the yellow coupler-containing layer in sample 101, respectively. Further, the same emulsion as that of Sample 101 except that the addition amount of the sensitizing dyes D, E, and F in the magenta coupler-containing layer was reduced by 25% (the amount of the adsorbent other than the dye was adjusted so that the coverage of the emulsion adsorbing compound did not change). The light-sensitive material 103 was manufactured using the same.

Sample 104 With respect to the silver chlorobromide emulsion A of the yellow coupler-containing layer in Sample 101, the sensitizing dyes A, B and C were added in an amount of 0 mol, 3.8 × 10 ^-4 mol and 0 mol, respectively. A light-sensitive material 104 was prepared using the same emulsion as in Sample 101 except that the moles were used (per mole of silver halide). Sample 105 Sample 1 was the same as Sample 101 except that the silver chlorobromide emulsion A of the yellow coupler-containing layer in Sample 101 was changed to the following emulsion (A-II).
A light-sensitive material 105 using the same emulsion as in Example No. 01 was produced. Sample 106 A light-sensitive material 106 was prepared using the same emulsion as Sample 101 except that the silver chlorobromide emulsion A of the yellow coupler-containing layer in Sample 101 was changed to the following emulsion (A-III).

<Preparation of Emulsion> Preparation of Emulsion (A-II) [{111} high silver chloride tabular grains (average grain size: 0.46 μm)] 2.0 g of sodium chloride and inert gelatin in 1.2 liters of water 2.8 g was added, and 45 cc of an aqueous silver nitrate solution (18 g of silver nitrate) and 45 cc of an aqueous sodium chloride solution (6.4 g of sodium chloride) were added to the vessel kept at 33 ° C. for 1 minute by a double jet method while stirring. End of addition 1
After one minute, 0.8 mmol of the following crystal habit controlling agent 1 and 560 g of a 10% aqueous solution of phthalated gelatin were added. One minute later, 3.0 g of sodium chloride was added. During the next 25 minutes, the temperature of the reaction vessel was raised to 60 ° C. After aging at 60 ° C. for 16 minutes, 3 g of sodium chloride and 1 × 10 ⁻⁵ mol of sodium thiosulfonate were added. Thereafter, 295 cc of an aqueous silver nitrate solution (18 g of silver nitrate) and 295 cc of an aqueous sodium chloride solution (50.3 g of sodium chloride and 2 × 10 5
^-8 mol of iridium hexachloride) and crystal habit controlling agent 1
160 cc of an aqueous solution (M / 50) was added over 13 minutes at an accelerated flow rate. Further, after 2 minutes, an aqueous solution of silver nitrate (34 g of silver nitrate) and an aqueous solution of sodium chloride (11.6 g of sodium chloride and 1.27 mg of yellow blood salt) were added over 5 minutes. Next, a 0.1 N thiocyanic acid solution 33.
5 cc and 0.32 mmol of sensitizing dye J, sensitizing dye K
Was added and 0.05 mmol of sensitizing dye L was added. The temperature was lowered to 40 ° C., and desalting was performed by a usual flocculation method. After washing with water, gelatin 67g
And 80 cc of phenol (5%) and 150 cc of distilled water. PH 6.2 with caustic soda and silver nitrate solution, pA
g was adjusted to 7.5. The resulting particles have a total projected area of 90
% Or more is 0.71 μm in average equivalent circle diameter and 0.1 in average thickness.
The particles were tabular grains having a diameter of 3 μm and an average equivalent sphere diameter of 0.46 μm. Crystal phase control agent 1

[0188]

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Preparation of Emulsion (A-III) [{100} High Silver Chloride Tabular Grains (Average Grain Size 0.47 μm)] In a reaction vessel, 1200 ml of H ₂ O, gelatin (methionine content of about 40 μmol / g) was added. 25 g of ionized alkali-treated bone gelatin), 0.4 g of sodium chloride, 1N nitric acid
4.5 ml of the solution was added (pH was 4.5), and the temperature was kept at 40 ° C. Next, Ag-1 solution (silver nitrate 0.2 g / cc) and X-
One liquid (sodium chloride 0.069 g / cc) was added and mixed at 48 cc / min for 4 minutes with vigorous stirring. After 15 seconds, an aqueous polyvinyl alcohol solution [polyvinyl alcohol (hereinafter referred to as PVA-1) having an average polymerization degree of vinyl acetate of 1700 and an average saponification rate of 98% or more to alcohol is used.
Containing 6.7 g and 1 liter of H ₂ O] in 150 ml
Was added. Further, 12.3 ml of a 1N nitric acid solution was added, and the pH was adjusted to 3.
Adjusted to 5. The temperature was raised to 75 ° C. in 15 minutes, 23 ml of 1N sodium hydroxide solution was added to adjust the pH to 6.5, and 1- (5
4.0 ml of -methylureidophenyl) -5-mercaptotetrazole (0.05%) and 4.0 m of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution).
1 was added. 4 g of sodium chloride was added, and the silver potential [vs.
Room temperature saturated calomel electrode] was adjusted to 100 mV, and while the Ag-1 solution and the X-1 solution were linearly increased from 40 cc / min to 42 cc / min as the growth process, the silver potential was kept at 100 mV for 15 minutes while maintaining the silver potential at the same time. Was added. Further, 12.5 ml of a 1N nitric acid solution was added to adjust the pH to 4.0. After adding 28.8 g of sodium chloride and setting the silver potential to 60 mV,
0.38 mmol of sensitizing dye J and 0.56 sensitizing dye K
Ag and 0.06 mmol of sensitizing dye L were added.
Solution 2 (0.1 g / cc of silver nitrate) and Solution X-2 0.0345 g / cc of sodium chloride at a flow rate of 40 cc / min.
After the addition, the mixture was left at 75 ° C. for 10 minutes.

Thereafter, the resultant was settled and washed at 40 ° C. to desalinate. Add 79 g of gelatin, redisperse the emulsion, p
H6.0 and pAg7.3. Then, a part of the emulsion is collected, and an electron microscope photograph image (TEM image) of the grain replica is taken.
Was observed. According to this, 90% of the projected area meter of all AgX grains is a tabular grain having a {100} major plane,
The average equivalent sphere diameter is 0.47 μm and the average particle thickness is 0.10.
μm, average aspect ratio 7.8, average adjacent side ratio 1.2
Met.

[0191]

Embedded image

2) Change in the total amount of gelatin Sample 102 The total amount of gelatin was 7.91 g by uniformly increasing the amount of gelatin binder in each layer of Sample 101 by 10%.
A light-sensitive material sample 102 identical to Sample 101 was prepared except that the ratio was changed to / m ² . Sample 107 The total gelatin amount was reduced from 6.88 g / m ² to 5.75 g / m ² by uniformly reducing the amount of gelatin binder in each layer other than the yellow coupler-containing layer in Sample 101 by 25%.
^The same photosensitive material sample 10 as sample 101 except that the sample was changed to ^2.
7 was produced. Sample 108 By reducing the amount of gelatin binder in each layer of Sample 101 uniformly by 30%, the total amount of gelatin was 4.82 g /
The same light-sensitive material Sample 1 and Sample 101 was changed to m ²
08 was produced.

3) Changing the order of coating the color-forming layers Sample 109 By changing the configuration order of the color-forming layers in Sample 101, the order of the yellow, magenta, and cyan color-forming layers from the side closer to the support was changed. A light-sensitive material sample 109 identical to Sample 101 was prepared except that the order of cyan, magenta and yellow color-forming layers was from the side closer to the support. Sample 110 The total gelatin amount was 6.88 g / m ² or 5.75 g / m ² by uniformly reducing the amount of gelatin binder in each layer other than the yellow coupler-containing layer in the light-sensitive material 109 by 25%.
It was changed to m ² was prepared in the same manner as the photosensitive material 110.

(2) Development processing and evaluation Each of the photosensitive material samples 101 to 110 was 127 mm
The film was processed into a roll having a width, and the following development test was performed using a minilab printer processor PP728 manufactured by Fuji Photo Film Co., Ltd. However, PP728 used was modified so that the processing time could be arbitrarily changed.

<Development Process-1> The processing steps are as follows. Processing time Temperature Color development 45 ° C 12 seconds Bleaching and fixing 40 ° C 12 seconds Rinse (1) ** 40 ° C 4 seconds Rinse (2) ** 40 ° C 4 seconds Rinse (3) ** 40 ° C 4 seconds Rinse ( 4) ** Drying at 40 ° C for 10 seconds (Note) ** Rinsing (4) to (1) in a 4-tank countercurrent system.

The composition of each processing solution is as follows. [Color developer] Water 800 ml Ethylenediaminetetraacetic acid 4.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triisopropanolamine 10.0 g Potassium chloride 10.0 g Potassium bromide 0.04 g Sodium p-toluenesulfonate 20.0 g Potassium carbonate 27.0 g Triazinyl diaminostilbene-based fluorescent brightener (Hakor FWA-SF manufactured by Showa Chemical Co., Ltd.) 3.5 g Sodium sulfite 0.1 g Disodium-N, N -Bis (sulfonatoethyl) hydroxylamine 10.0 g sodium triisopropylnaphthalene (β) sulfonate 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline-3 / Disulfuric acid / monohydrate 10.0 g water Additionally 1,000 ml pH (adjusted with 25 ° C. / potassium hydroxide and sulfuric acid) 10.25

[Bleach-fixing solution] Water 600 ml Ammonium thiosulfate (750 g / l) 110 ml ammonium sulfite 40 g ammonium ethylenediaminetetraacetate (III) ammonium 55 g ethylenediaminetetraacetic acid 5 g anhydrous citric acid 20 g Water was added to 1000 ml pH (25 ° C.) / Adjust with nitric acid and ammonia water) 5.5

[Rinse solution] Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

<Post-treatment> Next, a water washing step at 40 ° C. for 90 seconds.
Of the image obtained by the development processing I using a processing apparatus having
The materials 101 to 110 were further washed with water and dried.
The washing solution is the same as the new solution before the running process,
The structure of the water washing processing unit is the general processing used in the development processing II.
It has the same configuration as the water washing step of the apparatus. Developed samples 101-
In order to distinguish the sample from the sample 110,
1A to 110A. Sample 10 prepared as described above
1 to 110 and samples 101A to 110A,
The difference A value of the chromaticity before and after the post-processing defined in the above was determined. sand
Wachi, C-2000 color analyzer manufactured by Hitachi, Ltd.
And photographic paper samples developed with xenon common light sources
The exposed part was measured, and L^*a^*b^*
The colorimetric values on the chromaticity space were determined. Sample 101 after development processing
Colorimetric value (L^* ₁, A^* ₁, B^* ₁) And sample 101
Colorimetric value of A (L^* _Two, A^* _Two, B^* _Two) By post-processing
A = ｛L^* ₁-L^* _Two)^Two+ (A^*
₁-A^* _Two)¹+ (B^* ₁-B^* _Two)^Two｝^1/2By
I asked. Similarly, samples 102 to 110 and samples 102A to 102A
Table 3 shows the values of the color difference A before and after the post-processing determined from 110A.
It was shown to.

(Evaluation) Next, each sample was evaluated as follows. Image storability The density of yellow, magenta, and cyan at each density level of 0.25 and 1.0 in the gray (neutral color) portion was measured using a Macbeth densitometer (meeting the geometric conditions defined in the international standard ISO5 group, etc.). Densitometer). 500lx illuminance with white fluorescent lamp (emission color is equivalent to F8)
The density was also measured after irradiating this light for 7 days, and the density difference ΔD from before the irradiation (yellow, magenta, and cyan were defined as ΔDy, ΔDm, and ΔDc, respectively) was determined. The smaller the ΔD value, the better the image storability in a bright place. Further, a sensory evaluation was performed to evaluate the degree of change in gradation or color balance of a highlight portion such as skin color or background accompanying the fading in the above test. That is, an image having a human skin color and a bright background as the center of the pattern was prepared, and comparative observation evaluation was performed by observing the image before and after the fluorescent lamp irradiation test under the same conditions as above. The evaluation was performed by 15 standard observers who rated the skin color or background color balance change noticeably as "0". The change before and after the fluorescent lamp irradiation test was small and the connection of the skin tone after the irradiation was natural. Was evaluated as "1", and the intermediate evaluation was evaluated as "0.5". Three levels of evaluation points were given, and the average was determined. This value was used as the evaluation point. Table 4 shows the results.

[0201]

[Table 5]

The aging stability of the image of the present invention, that is, the effect of improving image storability, is remarkable on the highlight side (represented by the measured value of D = 0.25 in Table 4). Is remarkable in the relatively weak yellow and magenta color images (this portion is indicated by surrounding the frame).

From Table 4, it can be seen that Samples 103, 104 and 107
110 to 110, the color difference conditional expression [I] is satisfied, that is, the color difference from the post-processed sample is 2 or less (A value ≦ 2).
In this case, it is shown that the temporal stability of the image, particularly the light fastness of the image, is excellent. Among them, Samples 108 to 110 satisfy the conditional expression [II] for color difference, that is, A value ≦ 1, and in this case, the image storability (light fastness) to light irradiation is particularly excellent. That is, it is shown that the image storability is excellent when the characteristic value A of the color difference, which is the design concept of the photosensitive material and processing of the present invention, is designed to be 2 or less, preferably 1 or less. Looking at the relationship between the factors of each sample,
Samples Nos. 3 and 104 indicate that the image storability can be improved depending on the type of color sensitizer, Samples 107 and 108 indicate that it is effective to reduce the amount of gelatin, Samples 109 and 11
0 indicates that the structure in which the blue-sensitive emulsion layer is the uppermost layer is effective. In particular, Sample 110 shows that the effect obtained by combining the change in the layer order and the decrease in the amount of gelatin is additive. I have.

Dependence of Appearance of Gray (Neutral Color) Color Appearance on Light Source As a reference gray color development section, a color checker (GretagMacbeth-Color) manufactured by Gretar Macbeth Co., Ltd.
Checker) gray patch 8 (density 0.23),
Using gray patches 6.5 (density 0.44) and gray patches 5 (density 0.70), samples 101 to 110 were prepared using Macbeth densitometers to match the reference gray of each density. The development processing was performed using the processing machine and processing solution after the above-mentioned running test was performed.
Three kinds of viewing conditions were obtained for each of the developed samples obtained by printing the color checker sample including the above-mentioned gray patch portion, that is, a) a white fluorescent lamp F8 (a fluorescent lamp for color evaluation supplied by Toshiba Electric Co., Ltd.), b ) Comparing the colors under white fluorescent light F6 (same as above) and c) daylight (CIE-D6500),
The appreciation light source dependency of gray was evaluated. The evaluation was performed by 15 standard observers. "1" indicates that the viewing light source dependence is small and does not substantially cause discomfort, "0" indicates that the viewing light source dependence is large, and "0.5" indicates an intermediate evaluation of these. Evaluation points were given and represented by an average value. Table 5 shows the results.

[0205]

[Table 6]

Table 5 shows that the effect of the present invention is less dependent on the viewing light source for samples having a color difference A value of 2 or less, particularly 1 or less, before and after post-processing. It can be seen that Samples 107 and 108 having a composition of 6.0 g / m ² or less as described in the previous section provide particularly excellent results. Samples 103 and 104 in which the type of the color sensitizer was selected also showed that the image storability could be improved, and that the structure of Samples 109 and 110 in which the blue-sensitive emulsion layer was the uppermost layer was effective. In particular, sample 110 in which the change of the layer order and the decrease in the amount of gelatin are combined shows that the effect of the combination is additive.

Example 2 Samples 101 to 110 produced in Example 1 were used for development and evaluation. However, in the present embodiment, for the purpose of evaluating an example in which the A value is different depending on the developing method, the developing process I of the first embodiment is different from the developing process II as shown below.
Made changes to:

(2) Development processing and evaluation Each of the above photosensitive material samples 101 to 110 was 127 mm
The film was processed into a roll having a width, and the following development test was performed using a minilab printer processor PP728 manufactured by Fuji Photo Film Co., Ltd. However, PP728 used was modified so that the processing time could be arbitrarily changed. <
Development-II>

The processing steps are as follows. Processing process Temperature Time Color development 40 ° C 24 seconds Bleaching and fixing 40 ° C 24 seconds Rinse (1) ** 40 ° C 8 seconds Rinse (2) ** 40 ° C 8 seconds Rinse (3) ** 40 ° C 8 seconds Rinse ( 4) ** Dry at 40 ° C for 10 seconds ** Rinse (4) from (4) to (1) countercurrent type)

The composition of each processing solution is as follows. [Color developer] Water 800 ml Ethylenediaminetetraacetic acid 4.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triisopropanolamine 10.0 g Potassium chloride 10.0 g Potassium bromide 0.04 g Sodium p-toluenesulfonate 20.0 g Potassium carbonate 27.0 g Triazinyl diaminostilbene-based fluorescent brightener (Hakkoru FWA-SF, manufactured by Showa Chemical Co., Ltd.) 2.0 g Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 10.0 g Sodium triisopropylnaphthalene (β) sulfonate 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline-3 / 2 sulfuric acid / monohydrate 6.0g Triazinylamino diaminostilbene based fluorescent whitening agent adjusted with (Showa Kagaku Co.) manufactured Hakkoru FWA-SF) added 1.0g water 1000 ml pH (25 ° C. / potassium hydroxide and sulfuric acid) 10.25

[Bleaching-fixing solution] Water 600 ml Ammonium thiosulfate (750 g / l) 110 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g 5 g ethylenediaminetetraacetic acid 5 g 20 g of anhydrous citric acid / Adjust with nitric acid and ammonia water) 5.5

[Rinse solution] Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Next, using a processing apparatus having a water washing step at 40 ° C. for 90 seconds, the image sample 101 obtained by the development processing-II was obtained.
To 110 were further washed with water and dried. The method is the same as in the first embodiment. In order to distinguish them from the image samples 101 to 110, the samples that have been subjected to the post-processing are 101A to 110A. Samples 101 to 110 and Samples 101A to 110
For A, the A value defined in the present invention was determined according to the measurement method described in Example 1. Next, the same image storability as in Example 1 was evaluated for each sample. Table 6 shows the results.

[0214]

[Table 7]

Table 6 shows that the samples satisfying the condition of A value ≦ 2, more preferably A value ≦ 1, of the present invention have excellent image storability as in Example 1. Example 1
In the above, it was shown that the characteristic value (A value) of the color difference defined in the present invention can be set in a preferable range by changing the constituent factors of the light-sensitive material such as the amount of gelatin and the layer structure.
The effect of the photosensitive material factor is also seen in the results of Example 2. Further, in Example 2, the processing time and the concentration of the fluorescent whitening agent in the development processing, the addition of the fluorescent whitening agent to the bleach-fixing solution, and the change in the development processing factors such as the change in the concentration of the color developing agent also caused the color difference to be reduced. It is shown that a preferable range of the characteristic value (A value) can be determined, and in that case, an excellent effect also appears on the image storage characteristics. From the comparison between the results in Table 6 and Table 4 in Example 1, the light-sensitive material of the present invention was
In Example 1 in which the development processing time is short (the time required from the color development to the end of the rinsing step is 46 seconds), the effect on the comparative sample is large.

Example 3 A similar color developing solution (No. 1 shown below) was used, except that the fluorescent whitening agent used in the color developing solution of Example 1 was changed to the following compound.
~ 6) were prepared. Color developing solution No. Fluorescent brightener concentration (g / l) 1F-32.52F-132.53F-252.54 Comparative compound A 2.55 Comparative compound B 2.56-0 Running treatment The color developer of Example 1 later was replaced with Color Developer No. 1 and the samples 101, 104, 108, 11
0 development processing. Color developing solution No. 2-No. 5
The same developing process was performed except that the color developing solution was replaced. The A value for these samples was determined in the same manner as in Example 1. The same standard observer as in Example 1 performed sensory evaluation of the viewing light source dependence of the color balance of the developed sample and the change in color balance before and after the aging test. Table 7 shows the results. In Table 7, “gray balance” indicates color balance,
This is an expression in which the color balance is conscious of the deviation from the neutral color.

[0219]

[Table 8]

[0218]

Embedded image

From the results shown in Table 7, by selecting a fluorescent whitening agent to be added to the color developing solution, the color balance depends on the viewing light source depending on the combination of the photosensitive material constituted so as to satisfy the conditional expression of the present invention and the developing treatment. This shows that the storability is small and the image storability can be improved.

[0220]

The conditional expression [I], preferably the conditional expression [II]
The photographic light-sensitive material and the development processing method of the present invention, in which the photographic light-sensitive material and the development processing conditions are designed so as to satisfy the conditions, perform rapid development such as, for example, a color development time of, for example, 30 seconds or less, and even 14 seconds or less. Also image storability (stability over time)
, The change in the color balance of a highlight portion and a white background portion in particular is small, and the dependency of the image on the viewing light source can be reduced. Therefore, it is possible to provide a high-quality image with little change over time and little dependence on the viewing light source despite rapid processing.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroyuki Yoneyama 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film F-term (reference) 2H016 AB00 BC00 BC02 BK00 BK03 BL05 BM10

Claims (6)

[Claims] 1. A reflective support comprising at least a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler. In a color photographic light-sensitive material having one layer each, the chromaticity of an unexposed portion of the color photographic light-sensitive material after development processing satisfies the condition of the following conditional expression [I]. Photosensitive material. Conditional expression [I] 0 ≦ A ≦ 2 In conditional expression [I], A is defined by the following expression. A = ｛(L ^* ₁ −L ^* ₂ ) ² + (a ^* ₁ −a ^* ₂ ) ² +
(B ^* ₁ −b ^* ₂ ) ²で^1/2 where the values of L ^* ₁ , a ^* ₁ , b ^* ₁ , L ^* ₂ , a ^* ₂ , and b ^* ₂ are respectively the photosensitivity after the development processing. CIE1976 L ^* a ^* b ^* chromaticity (L ^* ₁₎ of the lowest density part of the material in the color space
a ^* ₁ b ^* _1), and represent the said surface color space system of chromaticity of the minimum density part after further subjected to post-processing to the photosensitive material after developing processing _{^{(L * 2 a * 2 b}} * 2) . However, post-processing is 3
A water washing treatment at 5 ° C. ± 5 ° C. for 90 seconds followed by drying. The tristimulus value used for the chromaticity standard is JI
S It is a value determined according to the method described in Z8717. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the chromaticity of the unexposed portion satisfies the condition represented by conditional formula [II]. Conditional expression [II] 0.1 ≦ A ≦ 1 3. The silver halide color photographic material according to claim 1, wherein the yellow coupler-containing layer is located farther from the support than the magenta coupler-containing layer and the cyan coupler-containing layer. 4. The method according to claim 1, wherein the total amount of the hydrophilic binder in the photographic component layer is 6.0 g / m ² or less.
4. The silver halide color photographic light-sensitive material according to any one of items 1 to 3, 5. A method for obtaining a color image through a step of at least one of color development, desilvering, washing and stabilization, and drying after imagewise exposing a silver halide color photographic light-sensitive material. The color development time of the silver halide color photographic light-sensitive material according to any one of the above items 4 to 3 seconds to 14 seconds, and all processing steps from the start of color development to the end of drying are 10 seconds to 90 seconds. A color image forming method comprising: 6. The color image forming method according to claim 5, wherein at least one processing step is performed in the presence of at least one compound represented by the following general formula (F). Embedded image (In the general formula (F), L ¹ and L ² may be the same or different and are represented by —OR ¹ or —NR ² (R ³ ), and the four substituents L in the general formula (F) ¹ and L ² are selected from substituents of the group represented by formula (II), wherein R ¹ and R ² are each a hydrogen atom, an alkyl group, or a substituent of the group represented by the following formula (II). R ³ represents an alkyl group or an alkyl group having a substituent of the group represented by the following formula (II), and M represents a hydrogen atom, an alkali metal, a tetraalkylammonium or a pyridinium. . Formula _{(II) -SO 2 M, -OSO} 2 M, -COOM, -N (R) 3
X (In the formula (II), X represents a halogen, and R represents an alkyl group.
M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium).