JPH0659421A - Color picture forming method - Google Patents

Abstract

PURPOSE:To form a color picture having high sharpness and maximum picture density even by ultrahigh-speed processing and reduced in residual color. CONSTITUTION:A photosensitive silver halide emulsion layer is provided on at least one side of a substrate to constitute a silver halide color photographic sensitive material. The material is exposed, color-developed, bleached, fixed, washed with water and/or stabilized and then dried to form a color picture. The substrate on the emulsion layer side is coated with a hydrophilic colloid layer in which >=20wt.% of a white pigment is filled at >=2g/m<2>, and at least one silver halide emulsion layer contains >=90mol% of silver chloride. The photosensitive material is color-developed within 5 to 30 sec to form a color picture.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a color image forming method using a silver halide color photographic light-sensitive material. Especially in the color print processing method that shortens the processing time,
The present invention relates to a color image forming method capable of providing a color image having excellent sharpness.

[0002]

2. Description of the Related Art For silver halide color photographic light-sensitive materials, especially for light-sensitive materials for viewing such as light-sensitive materials for printing, it has been required in recent years to provide higher quality images with higher productivity. ing. For this reason, in the development process, in order to improve efficiency, in recent years, the development process has been shortened and the photosensitive material has been improved by improving the development recipe, improving the processing equipment, and the like. Examples of a method for speeding up the processing by improving the light-sensitive material include WO 87-0453.
No. 4 using a silver halide light-sensitive material having a high content of silver chloride and treating with a color developing solution containing substantially no sulfite ion and benzyl alcohol.
It discloses a method of shortening the color development time required for one minute or more to one minute or less. Further, as a method of ultra-acceleration in which the color development time is further shortened, there is generally known a method of using a silver halide light-sensitive material having a high silver chloride content and performing the development processing with a developer having a high pH or a high processing temperature. For example, JP-A-3-109549 and JP-A-4-4
No. 43 is available.

On the other hand, as one of the performances of the light-sensitive material required to obtain a high quality print as in the present invention, it is known that excellent image clarity is particularly important. The sharpness of an image can be expressed numerically as, for example, the sharpness, and as a method for improving this, an anti-irradiation dye for reducing the scattering of incident light in the photosensitive layer at the time of exposure is previously made hydrophilic. A method of dispersing in a colloid layer and a water-resistant layer provided on the surface of the support in order to reduce scattering of incident light on the support surface during exposure and reduce image bleeding due to scattering of incident light during image observation after processing. A method for increasing the white pigment loading is generally known.
Regarding the former, examples of improved anti-irradiation dyes are disclosed in JP-A-62-283336 and Research Disclosure RD-17643 (December 1987).
Mon, 22), RD-18716 (11 November 1979)
Month, Item 647) and the like. Regarding the latter, examples of improved polyethylene layers containing titanium oxide are disclosed in JP-B-58-43734 and JP-A-61-25.
9246 and the like. In addition, a hydrophilic binder layer is provided on the surface of the support, and colloidal silver,
There is also a method of improving the sharpness by incorporating a solid fine particle dye or a white pigment, for example, the method described in JP-A-3-127058. Therefore,
According to the technique as described above, it is possible to obtain an image having a high sharpness within a color development time of 1 minute or less, and as an example in which the color development time of 45 seconds can be realized, for example, Japanese Patent Laid-Open No. Hei 3
There is a method described in No. 38640.

However, when the processing time is shortened to 30 seconds or less (hereinafter referred to as "ultra-rapid processing") according to the above-mentioned method and a color image having high sharpness is formed, color contamination (hereinafter , Which is referred to as residual color), and other problems such as deterioration of white background and insufficient image density. For example, Japanese Patent Laid-Open No. 3-156
When ultra-rapid processing is performed by using a light-sensitive material containing an anti-irradiation dye in a hydrophilic colloid layer according to the method described in No. 454, remarkable residual color is accompanied as an adverse effect in order to obtain high sharpness. There was found. Further, when an image is formed by ultra-rapid processing using a photosensitive material provided with a hydrophilic colloid layer containing a solid fine particle dye on the surface of the support by the method described in JP-A-3-38640, the sharpness is Although it is improved, it has been found that deterioration of the residual color and further reduction of the maximum color density occurs in the yellow color forming layer depending on the processing conditions. It was also found that the maximum color density was lowered in the yellow color forming layer when a photosensitive material provided with a hydrophilic colloid layer containing colloidal silver was used instead of the solid fine particle dye. On the other hand, when a hydrophilic colloid layer containing a white pigment was provided, it was found that there was no problem of residual color, but there was a decrease in the maximum color density similar to the above depending on the coating amount of the white pigment and the hydrophilic colloid layer. . Further, for example, in the method of incorporating a white pigment in the water resistant resin layer described in JP-A-3-221942, when the content of the white pigment in the water resistant resin layer is increased in order to improve the sharpness, the water resistance of a smooth surface is improved. It is practically difficult to obtain a sufficient sharpness because it is difficult to form the functional resin layer.

[0005]

As is apparent from what has already been described, an object of the present invention is to provide a high quality color image in a highly productive color print with a reduced processing time. In particular, a color image forming method that shortens the processing time, specifically, provides a color print with high sharpness, high maximum density, and less residual color and good white background even if color development is within 30 seconds To provide.

[0006]

Means for Solving the Problems The present inventor has investigated the above problems by using a light-sensitive material in which various colored hydrophilic colloid layers are coated on a support. As a result, it was found that when a white pigment is used, a sufficient maximum color density can be obtained even in a shorter development time than in the past, and the present invention as described below was achieved by developing this finding. (1) After imagewise exposure of a silver halide color photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, it is subjected to color development, bleaching / fixing and washing and / or stabilizing steps. In the method of forming a color image by drying, 2 g / m ² or more of white pigment is contained on the support on the side having the photosensitive silver halide emulsion layer in a white pigment loading of 20% by weight.
At least one of the silver halide emulsion layers coated with the above hydrophilic colloid layer has a silver chloride content of 90 mol.
% Of a silver halide emulsion is subjected to color development in 5 to 30 seconds. (2) After the image exposure of a silver halide color photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, it is subjected to color development, bleaching / fixing and washing and / or stabilizing steps. In the method of forming a color image by drying, 2 g / m ² or more of white pigment is contained on the support on the side having the photosensitive silver halide emulsion layer in a white pigment loading of 20% by weight.
A colored layer coated with the above hydrophilic colloid layer and capable of being decolorized by a development process, for example, a hydrophilic colloid layer containing colloidal silver and / or a hydrophilic colloid layer containing a solid fine particle dye, and The photosensitive material is 400
has an optical reflection density (when unexposed) of 0.2 to 2.0 at the wavelength having the highest optical density in the visible light region of nm to 700 nm, and at least one of the silver halide emulsion layers has silver chloride. A color image forming method, which comprises color-developing a light-sensitive material containing a silver halide emulsion having a content of 90 mol% or more in 5 to 30 seconds. (3) The film thickness of the photographic constituent layer coated on the support reaches 1.5 times or more the dry film thickness in 30 seconds in a color developing solution. (1) or (2) The described color image forming method. (4) The color image forming method as described in (1), (2) or (3), wherein the developing agent used in the color developing solution is represented by the following general formula (D).

[0007]

[Chemical 2]

(5) The processing time of the light-sensitive material is characterized in that the bleach-fixing process is within 25 seconds, and the time from the beginning of the developing process to the end of the drying process is within 120 seconds (1).
The method for forming a color image according to item (2), (3) or (4).

When a hydrophilic colloid layer containing a white pigment is provided on a support, in order to obtain high sharpness,
The amount of white pigment applied must be ² g / m ² or more. It is preferably 4 g / m ² or more, more preferably 8 g / m ² or more and 20 g / m ² or less. The weight of the white pigment referred to in the present invention is an amount including the weight of the white pigment when it contains various surface treatment agents or dispersion stabilizers for the purpose of improving the dispersibility of the white pigment. . The content of the white pigment in the hydrophilic colloid layer containing the white pigment is 20% by weight or more, preferably 40% by weight or more, and more preferably 70% by weight or more and 98% by weight or less within the range satisfying the above conditions. is there. If the content of the white pigment is less than 20% by weight, it is difficult to obtain the effect on the sharpness, and the maximum color density tends to decrease, which makes it difficult to achieve the object of the present invention. On the other hand, if it exceeds 98%, it becomes substantially difficult to form a layer. The thickness of the hydrophilic colloid layer containing the white pigment is determined by the coating amount of the hydrophilic colloid layer and the content rate of the white pigment, but is preferably 0.5 to 10 μm. The white pigment used in the present invention includes titanium dioxide, barium sulfate, lithopone, white alumina, calcium carbonate, white silica, antimony trioxide, titanium phosphate,
Examples thereof include zinc oxide, lead white and gypsum. Among these pigments, the use of titanium dioxide is particularly effective. Titanium dioxide may be of rutile type or anatase type, and may be produced by any of the sulfate method and chloride method.

The white pigment particles used in the hydrophilic colloid layer may have an average particle size of 0.1 to 1.0 μ. Preferably 0.
2 to 0.3 μ. In the present invention, gelatin can be preferably used as a binder for the hydrophilic colloid layer containing a white pigment, the silver halide emulsion layer, the non-photosensitive intermediate layer and the like. If desired, other hydrophilic colloids may be used in place of gelatin in any proportion. Examples thereof include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin or casein, cellulose derivatives (eg, hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate), sodium alginate and starch derivatives. Saccharides, polyvinyl alcohol, partial acetals of polyvinyl alcohol, poly (N-vinylpyrrolidone), polyacrylic acid,
There may be mentioned a wide range of synthetic polymers such as polymethacrylic acid, polyacrylamide, polyvinyl imidazole and polyvinyl pyrazole. In the present invention, the white pigment-containing hydrophilic colloid layer may contain various materials added to the photographic light-sensitive material, in addition to the white pigment and the binder. For example, it is a surfactant as a coating aid, a hardener, a dye, or an antifoggant. Furthermore, a high-boiling point organic solvent dispersed on fine oil droplets can be contained. When the dispersion of the high-boiling point organic solvent is contained, it is preferable that various oil-soluble materials are dissolved and contained therein.

The light-sensitive material of the present invention comprises a support, at least one light-sensitive emulsion layer coated thereon, a non-light-sensitive layer such as a color mixing prevention layer and a protective layer, and a hydrophilic material containing a white pigment. And a colloidal layer. In the present invention, the hydrophilic colloid layer containing the white pigment is provided between the support and the photosensitive emulsion layer. As the support used in the present invention, paper made of natural pulp or synthetic pulp, baryta paper, polyethylene, resin coated paper coated with polyolefin such as polypropylene or polyester, polyethylene, polypropylene, polystyrene,
Examples thereof include synthetic polymer films such as polycarbonate, rigid vinyl chloride and polyethylene terephthalate, and natural polymer films such as cellulose diacetate, cellulose triacetate and nitrocellulose. From the viewpoint of accelerating the development processing of the light-sensitive material, the support preferably has water resistance. That is, it is preferable to use water resistant resin coated paper or polymer film. It is also possible to use a support having a surface of diffuse reflection of the second kind.
The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the surface of the second class diffuse reflection has a three-dimensional average roughness of 0.1 to the center plane.
It is 2 μm, preferably 0.1 to 1.2 μm. The frequency of the surface irregularities is preferably 0.1 to 2000 cycles / mm for irregularities having a roughness of 0.1 μm or more,
Further, it is preferably 50 to 600 cycles / mm. For details of such a support, see JP-A-2-2.
No. 39244.

In the present invention, the white pigment is contained only in the hydrophilic colloid layer containing the white pigment, and the resin constituting the support, for example, the resin coating the paper base or the resin film which is the support itself is contained. It is possible to use a mode in which the white pigment is not contained, or a mode in which the white pigment is contained also in the resin constituting the support in addition to the hydrophilic colloid layer containing the white pigment.

A photosensitive emulsion layer may be directly provided on the hydrophilic colloid layer containing a white pigment, or a photosensitive emulsion may be formed through one or a plurality of non-photosensitive hydrophilic colloid layers. You may install layers. When a non-photosensitive hydrophilic colloid layer is provided, the total thickness of these layers is 5
It is preferably μ or less. Further, it is preferably 2 μm or less. These non-photosensitive hydrophilic colloid layers can contain various photographically useful substances, if necessary. For example, it is a surfactant as a coating aid, a hardener, a dye, or an antifoggant. Further, a coloring layer capable of being decolorized during development processing can be constituted by containing colloidal silver, a dye dispersed in a solid state, a dye dyed with a cationic polymer or the like. Alternatively, a high-boiling point organic solvent dispersed in the form of fine oil droplets may be contained.
In these solvents, a photographically useful substance such as an oil-soluble color mixing inhibitor, a fluorescent whitening agent or an ultraviolet absorber can be dissolved and contained.

The color layer which is preferably used as the non-photosensitive hydrophilic colloid layer and which can be decolorized by the development treatment may be in direct contact with the emulsion layer, and may be an intermediate layer containing a treatment color mixture preventing agent such as gelatin or hydroquinone. You may arrange | position so that it may contact through. This colored layer needs to be provided as a lower layer (on the side of the support) of the emulsion layer having a sensitivity in a region that substantially overlaps with the light wavelength region absorbed by the colored substance. It is possible to individually install all of the colored layers corresponding to the emulsion layers sensitized to have sensitivity in different wavelength regions, or to selectively install some of them.
It is also possible to provide a coloring layer having absorption in a wide wavelength range so as to correspond to a plurality of emulsion layers having different sensitizing wavelength ranges.

A conventionally known method can be applied to form the colored layer. For example, a method of dispersing a fine powder of a dye in a solid state, a method of mordanting an anionic dye on a cationic polymer, a method of adsorbing the dye to fine particles such as silver halide and fixing it in a layer, a method of using colloidal silver. And so on. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at a pH of 6 or lower but is substantially water-soluble at a pH of 8 or higher is disclosed in Japanese Patent Laid-Open No. 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable. In the present invention, the preferred amount of the fine powder dye is ^{0.001g / m 2 ~5.0g / m 2} , more preferably from ^{0.005g / m 2 ~0.5g / m 2} . The preferred amount of colloidal silver used is 0.001 g.
/ M ^{2 to} 5.0 g / m ² , more preferably 0.01
a ^{g / m 2 ~1.5g / m 2} .

In the light-sensitive material relating to the present invention, a hydrophilic colloid layer is formed on pages 27 to 76 of European Patent EP 0337490A2 for the purpose of preventing irradiation and halation and improving safety of safelight. It is preferable to add a dye that can be decolorized by the described treatment (in particular, an oxonol dye and a cyanine dye). In particular,
Water-soluble dyes described in Japanese Patent Application No. 03-310139 are preferable as dyes that are less likely to deteriorate color separation and safelight safety even if the amount used is increased. The preferable coating amount of these water-soluble dyes can be the following coating amount as one guide. Cyan dye: 20 to 100 mg / m ² Magenta dye: 0 to 50 mg / m ² Yellow dye: 0 to 30 mg / m ^{2 In the} present invention, coating or coating of a coloring layer containing solid fine particle dye or colloidal silver as described above or It is preferable to color the hydrophilic colloid layer with / and a water-soluble dye. The optical reflection density of the unexposed light-sensitive material used in the present invention is such that the optical reflection density at a wavelength having the highest optical reflection density in the visible region of 400 nm to 700 nm as a light wavelength is 0.2 or more and 2.0 or less. Is more preferable, 0.2 or more and 1.5 or less, and especially 0.
It is preferably 2 or more and 1.2 or less, and the type and coating amount of the coloring substance (for example, white pigment, solid fine particle dye, anti-irradiation dye, colloidal silver, etc.) can be selected within a range satisfying this condition. In the region where the optical reflection density is less than 0.2, the effect of the coloring substance on the sharpness cannot be substantially expected. The optical reflection density is 2.0
In the above range, the white background is significantly deteriorated due to the residual color, which is not suitable for practical use. The optical reflection density in the present invention is measured by a reflection densitometer generally used in the art, and is defined as follows. However, at the time of measurement, it is necessary to install a standard reflection plate on the back surface of the sample to prevent a measurement error due to light trying to pass through the sample. Optical reflection density = log ₁₀ (F ₀ / F) F ₀ : Reflected light flux of standard white plate F: Reflected light flux of sample

In the color light-sensitive material of the present invention, at least one yellow color forming silver halide emulsion layer, magenta color forming silver halide emulsion layer and cyan color forming silver halide emulsion layer are coated on a reflective support. Can be configured.
In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color forming layers described above, and are also formed on the support in the order described above. It can be constructed by coating. However, the order may be different from this. That is, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the silver halide grains having the largest average grain size comes to the uppermost layer,
From the viewpoint of storage stability under light irradiation, it may be preferable to use the magenta color photosensitive layer as the lowermost layer. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

The silver halide grains used in the present invention include silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like. In particular, in the present invention, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less (including zero), preferably 0.2 mol% or less (including zero). On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing storage stability of a light-sensitive material, 0.01 to 3 mol% on the emulsion surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (shell)
Grain having a so-called laminated structure having a different halogen composition with [one or more layers] or a structure having a portion having a different halogen composition in a non-layered manner inside or on the surface of the particle (edge, corner or surface of the particle when present on the surface of the particle) Particles having a structure in which portions having different compositions are bonded to each other can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing as in the present invention. In the present invention, the silver chloride content of the high silver chloride emulsion is preferably 90 mol% or more, more preferably 95 mol% or more. In such a high silver chloride emulsion, a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above is preferable. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. The silver bromide content of the localized silver bromide phase is analyzed using an X-ray diffraction method (for example, described in "Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis" Maruzen). can do. These localized phases can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example thereof is that epitaxially grown on the corners of the particles. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is regular (regulous, such as cubic, tetradecahedral or octahedral).
It is possible to use those having an ar) crystal form, those having an irregular crystal form such as spheres and plates, or those having a composite form thereof. It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is P. Glafki.
des by Chimie et Phisique Photographique (Paul Mont
published by el, 1967), by GF Duffin Photographic Em
ulsion Chemistry (Focal Press, 1966), V.
Making and Coating Photographic by L. Zelikman et al
It can be adjusted using the method described in Emulsion (Focal Press, 1964) and the like. That is,
Any method such as an acidic method, a neutral method, an ammonia method, etc. may be used.As a method for reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. Is also good. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains a different metal ion or a complex ion thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions. Ions mainly selected from iridium, rhodium and iron or their complex ions in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel and iron as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of a silver salt or other aqueous solution, or in the form of fine silver halide grains containing metal ions in advance and dissolving the fine grains. It is contained in the localized phase and / or other particle portion (matrix). The metal ion used in the present invention can be incorporated into the emulsion grains either before grain formation, during grain formation, or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, and tellurium sensitization with a tellurium compound are performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface. To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A-62-215272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanine by FM Harmer.
dyes andrelated compounds (John Wiley & Sons New
The thing described in York, London company 1964) can be mentioned. As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-12 is known.
The spectral sensitizing dye described in No. 3340 is very preferable from the viewpoint of stability, strength of adsorption, temperature dependence of exposure and the like.

In the case of efficiently spectrally sensitizing the infrared region of the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15 Lower left column, EP-0,420,011
No. 4, line 21 to page 6, line 54, EP-0, 420, 012
No. 4, page 12, line 10 to page 33, EP-0,443,46
The sensitizing dyes described in US Pat. No. 6, US-4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes into a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-
As described in 22089 and the like, an acid or a base is allowed to coexist to prepare an aqueous solution, and as described in U.S. Pat. No. 3,822,135 and U.S. Pat. It may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent that is substantially immiscible with water, such as phenoxyethanol, and then dispersed in water or a hydrophilic colloid to add to the emulsion. JP-A-53-102733, JP-A-58-105141
Alternatively, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 628969 and No. 4225666.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. adding some prior to chemical sensitization and the rest after chemical sensitization. It is possible and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column, may be used in combination. preferable. By using these compounds, the storability of the light-sensitive material, the processing stability, and the supersensitizing effect can be specifically enhanced. Of these, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are 0.5 × 10 ⁻⁵ mol to 5.0 × 10 ⁵ mol per mol of silver halide.
^-2 mol, preferably 5.0 x 10 ^-5 mol to 5.0 x 10
An amount of ^-3 mol is used, and an advantageous amount is in the range of 0.1 times to 10,000 times, preferably 0.5 times to 5000 times, per mol of the sensitizing dye.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, it is preferable to use low calcium gelatin having a calcium content of 800 ppm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

The swelling of the hydrophilic colloid layer consisting of the emulsion layer, the non-photosensitive layer and the like coated on the support of the color photographic light-sensitive material of the present invention in the color developer achieves the object of the present invention. Therefore, it is necessary to be prompt. Specifically, the film thickness during color development is the value of the film thickness when the photosensitive material is immersed in an alkaline aqueous solution at 40 ° C., and the film thickness after 30 seconds is 1.5 times or more the dry film thickness. Is preferably reached. It is preferably 1.5 times or more in 20 seconds, more preferably 1.5 times or more in 10 seconds. Also preferably 5
It is less than twice. Such a magnification can be easily set by a method of changing the type and amount of the hardener used in the hydrophilic colloid layer. The dry film thickness here is the value of the film thickness measured under the conditions after the photosensitive material was stored under the conditions of 25 ° C. and humidity of 55% for 2 hours or more. Further, the alkaline aqueous solution referred to here is 0.2 mol /
1 liter of sodium hydrogen carbonate (pH 10.
(Adjusted to 0) represents an aqueous solution.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance exposure. As a preferred exposure method for high illuminance exposure, there is a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds, more preferably shorter than 10 ⁻⁶ seconds. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

Cyan, magenta, or yellow couplers are impregnated into rollable latex polymers (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents listed in the table above. Then, it is preferable to dissolve in a polymer soluble in an organic solvent and to emulsify and disperse in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in US Pat. No. 4,857,449, columns 7 to 15 and International Publication WO88 / 00723, page 12 to.
The homopolymer or copolymer described on page 30 can be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, particularly acrylamide-based polymer, from the viewpoint of color image stability and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent No. EP 0277589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, by chemically bonding with the aromatic amine-based developing agent remaining after color development processing,
When chemically bound to the compound (F) in the above-mentioned patent specification which forms a chemically inert and substantially colorless compound, and / or an oxidant of an aromatic amine color developing agent remaining after the color developing treatment. The use of the compound (G) in the above-mentioned patent specification, which forms a chemically inert and substantially colorless compound, simultaneously or alone, is effective in, for example, the residual color developing agent in a film in the storage after processing or its developing agent. It is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the oxidant and the coupler.

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in Japanese Patent No. 33144, European Patent EP 0333185A2.
3-hydroxypyridine type cyan couplers described in the above specification (in particular, the couplers listed as specific examples (4
(2) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, and couplers (6) and (9) are particularly preferable)
And cyclic active methylene cyan couplers described in JP-A No. 64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable), and European Patent No. EP 0456226A1. Pyrrolopyrazole type cyan coupler, European Patent EP044890
Pyrroylimidazole type cyan couplers described in No. 9, European Patent Nos. EP0488248 and EP04911.
Preference is given to using the pyrrolotriazole type cyan couplers described in 97A1. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969
Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in A1 specification, Arondianilide type yellow couplers having a cyclic structure described in European Patent EP 0482552A1, US Pat. The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

As the magenta coupler used in the present invention, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the above-mentioned publicly known documents are used, and among them, hue, image stability,
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of a pyrazolotriazole ring as described in JP-A-61-65245 in terms of color developability, etc. -65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and Europe. Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785.

The processing method of the color light-sensitive material of the present invention is as follows:
In addition to the methods described in the above table, 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, lines 17 to 18 The processing materials and processing methods described in the lower right column, line 20 are preferable.

The processing material and processing method used in the present invention will be described in detail. In the present invention, the light-sensitive material is color-developed, desilvered, washed with water or stabilized. The color developing solution used in the present invention contains a known aromatic primary amine developing agent. A preferred example is p
-A phenylenediamine derivative, a typical example of which is
N, N-diethyl-p-phenylenediamine, 4-amino-N, N-diethyl-3-methylalinine, 4-amino-N- (β-hydroxyethyl) -N-methylaniline, 4-amino-N-ethyl. -N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (β-
Hydroxyethyl) -3-methylaniline, 4-amino-N-ethyl-N- (3-hydroxypropyl) -3-
Methylaniline, 4-amino-N-ethyl-N- (4-
Hydroxybutyl) -3-methylaniline, 4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline, 4-amino-N, N-diethyl-3- (β-hydroxyethyl) ) Aniline, 4-amino-N-ethyl-N- (β-methoxyethyl) -3-
Methylaniline, 4-amino-N- (β-ethoxyethyl) -N-ethyl-3-methylaniline, 4-amino-
N- (3-carbamoylpropyl) -N-n-propyl-3-methylaniline, 4-amino-N- (3-carbamoylbutyl) -Nn-propyl-3-methylaniline, N- (4-amino -3-Methylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine, N-
(4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide. Particularly preferred compounds are those represented by the above general formula (D). This specific example is shown, but the present invention is not limited to this.

[0044]

[Chemical 3]

[0045]

[Chemical 4]

[0046]

[Chemical 5]

The most preferred compounds are 4-amino-N-ethyl-N- (3-hydroxypropyl) -3-methylaniline, and 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methyl. It is aniline. In addition, salts of these p-phenylenediamine derivatives and sulfates, sulfites, hydrochlorides, naphthalenedisulfonates, p-toluenesulfonates and the like may be used. The amount of the aromatic primary amine developing agent used is preferably 0.002 mol to 0.2 mol, and more preferably 0.005 to 0.1 mol, per liter of the developing solution. The developing time of the color developing process which can be generally applied is 45 seconds to 3 minutes, but the shorter one is preferable in the invention for the purpose of achieving speeding up. Specifically, 10 seconds to 25 seconds are preferable. The treatment temperature at that time is 20 to 50 ° C, preferably 30 to 45 ° C, and most preferably 37 to 42 ° C. The replenishment amount is preferably small, but ^{20 to} 600 ml is appropriate per 1 m ^{2 of} the light-sensitive material, preferably 30 to 200 ml, more preferably 4
It is 0 to 100 ml. In the present invention, the processing time (for example, developing time) means the time from when the photosensitive material enters the target processing solution to when it enters the next processing solution. The term "from the beginning of the developing process to the end of the drying process" means the time from entering the developing bath of the developing processing apparatus to passing through the drying step to the outside of the apparatus.

In practicing the present invention, it is preferable that substantially no benzyl alcohol is contained. The term "substantially free from" means that the concentration of benzyl alcohol is preferably 2 ml / liter or less, more preferably 0.5 ml / liter or less, and most preferably, benzyl alcohol is not contained at all.

The color developer used in the present invention suppresses fluctuations in photographic characteristics due to continuous processing, and substantially does not contain sulfite ion in order to achieve the effects of the present invention. That is, the sulfite ion concentration is 3.0 × 10 ⁻³ mol / liter or less. Sulfite ion is preferably 1.0 × 10 ⁻³ mol / liter or less, and most preferably contains no sulfite ion. However, in the present invention, however, a very small amount of sulfite ion used for the antioxidant of the processing agent kit in which the developing agent is concentrated before preparing the use solution is excluded. The color developing solution used in the present invention should further contain substantially no hydroxylamine in order to suppress fluctuations in photographic characteristics due to fluctuations in the concentration of hydroxylamine. 5.0 × 10 ⁻³ mol / liter or less) is more preferable. Most preferably, it contains no hydroxylamine at all.

The color developer used in the present invention more preferably contains an organic preservative in place of the hydroxylamine or sulfite ion. Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, it is an organic compound having a function of preventing oxidation of a color developing agent due to air or the like, but among them, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyl. Ketones,
Organic preservatives in which α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. are particularly effective Is. These are disclosed in JP-B-48-30496 and JP-A-52.
143020, 63-4235, 63-30
No. 845, No. 63-21647, No. 63-44655.
63, 53-55131, 63-43140, 63-56654, 63-58346, 63-.
43138, 63-146041, 63-44.
657, 63-44656, U.S. Pat. No. 3,61.
5,503, 2,494,930, JP-A-1-9
7953, 1-186939, 1-18694
No. 0, No. 1-187557, No. 2-306244, etc. Other preservatives include JP-A-57
-44148 and 57-53749, various metals, salicylic acids described in JP-A-59-180588, JP-A-63-239447, and JP-A-63-128.
340, JP-A-1-186939 and 1-1875.
Amines as described in JP-A-57-35,
No. 32 alkanolamines, JP-A-56-94
Polyethyleneimines described in U.S. Pat.
You may use the aromatic polyhydroxy compound etc. of 746,544 etc. as needed. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as N, N-diethylhydroxylamine and N, N-di (sulfoethyl) hydroxyamine,
It is preferable to add a hydrazine derivative (excluding hydrazine) such as N, N-bis (carboxymethyl) hydrazine or an aromatic polyhydroxy compound represented by sodium catechol-3,5-disulfonate. In particular, it is more preferable to use the dialkylhydroxylamine and / or hydrazine derivative in combination with the alkanolamines from the viewpoint of improving the stability of the color developing solution, and thus improving the stability during continuous processing.

In the present invention, it is preferable that the color developer contains chlorine ions in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter. Particularly preferably 3.5 × 10 ^-2
˜1.0 × 10 ⁻¹ mol / liter. When the chlorine ion concentration is more than 1.5 × 10 ^{-1 to} 1.0 × 10 ^-1 mol / liter, it has a drawback that development is delayed, and in order to achieve the object of the present invention that the concentration is high and the maximum concentration is high. Not preferable. If it is less than 3.0 × 10 ^-2 mol / liter,
It is not preferable for preventing fog. In the present invention,
It is preferable that the color developer contains 0.5 × 10 ⁻⁵ mol / liter to 1.0 × 10 ⁻³ mol / liter of bromine ions. More preferably, 3.0 × 10 ^{−5 to} 5 × 10
^-4 mol / l. Bromine ion concentration is 1 × 10 ^-3
When the amount is more than mol / liter, the development is delayed, the maximum density and the sensitivity are lowered, and when it is less than 0.5 × 10 ⁻⁵ mol / liter, fog cannot be sufficiently prevented.

Here, the chlorine ion and the bromine ion may be directly added to the color developing solution or may be eluted from the light-sensitive material to the color developing solution during the development processing. When added directly to the color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developing solution. As a source of bromide ions,
Examples thereof include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide and magnesium bromide. When it is eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution contains compounds of other known developing solution components. be able to. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, 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 salt, lysine salt and the like can be used. Particularly, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in a high pH range of pH 9.0 or more, and even when added to a color developing solution, they have excellent photographic performance. It is particularly preferable to use these buffers, since they have the advantages of being free from adverse effects (fogging, etc.) and being 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, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Examples thereof include potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate). The amount of the buffer added to the color developer is preferably 0.1 mol / liter or more, and particularly 0.1 mol / liter to 0.1.
It is particularly preferably 4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for 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'-tetramethylenephosphonic acid, trans-silohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2
-Hydroxybenzyl) ethylenediamine-N, N'-
Examples thereof include hydroxyethyliminodiacetic acid diacetate.
Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per liter.

If desired, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication No. 37
-16088, 37-5987, 38-782.
No. 6, No. 44-12380, No. 45-9019, and thioether compounds represented by US Pat. No. 3,813,247;
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
No. 0074, JP-A Nos. 56-156826 and 52-
Quaternary ammonium salts represented by U.S. Pat. No. 4,434,29, U.S. Pat. Nos. 2,494,903 and 3,128,182.
No. 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, US Pat. No. 2,48
2,546, 2,596,926 and 3,58
Amine compounds described in 2,346, etc., JP-B-37-
16088, 42-25201, U.S. Pat.
128,183, Japanese Patent Publication Nos. 41-11431, 42
-23883 and U.S. Pat. No. 3,532,501, and the like, polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, any antifoggant can be added, if desired. As the antifoggant, 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, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adanine. The color developer applicable to the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / liter, preferably 0.1 g
~ 4 g / l. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid polyalkyleneimine may be added.

After color development, desilvering processing is performed. In the desilvering process, the bleaching process and the fixing process may be separately performed,
It may be performed at the same time (bleach-fixing process). In the mode of the desilvering process in the present invention, a bleach-fixing process is preferable for the purpose of simplifying the process and shortening the time. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out.

Examples of the bleaching solution used in the bleaching solution and the bleach-fixing solution include iron salts; compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II); peracids. Quinones; nitro compounds and the like. Typical bleaching agents are iron chloride; ferricyanide; dichromate; iron (I
II) organic complex salts (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid) Persulfate; bromate; permanganate; nitrobenzenes and the like. Of these, iron ethylenediamine tetraacetate
(III) Complex salt, and iron 1,3-diaminopropane tetraacetate (I
II) Complexing salts and other iron (III) aminopolycarboxylic acid complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. A bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is used at a pH of 3-8.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; metal corrosion inhibitors such as ammonium sulfate are added to the bleaching solution and the bleach-fixing solution. be able to. In the bleaching solution and bleach-fixing solution, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (pK
a) is a compound of 2 to 5.5, and specifically, acetic acid, propionic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, in the fixing solution and the bleach-fixing solution, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N ', N') are used for the purpose of stabilizing the solution. -Ethylenediaminetetraphosphonic acid) is preferred.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. Bleach,
If necessary, a bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof. Specific examples of useful bleaching accelerators include U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
And Research Disclosure No. 17129 (July 1978) and the like having a mercapto group or a disulfide bond;
Thiazolidine derivatives described in No. 29; US Pat. No. 3,7
Thiourea derivatives described in JP-A No. 06,561;
Iodide salt described in 16235; West German Patent No. 2,74
The polyoxyethylene compounds described in No. 8,430; the polyamine compounds described in JP-B-45-8836; the bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material.

For the purpose of shortening the processing time, the total time of the bleaching / fixing step in the present invention is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 5 seconds to 1 minute, more preferably 5 seconds to 25 seconds. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the generation of stains after the processing is effectively prevented. Further, in the treatment step of the present invention, the stirring method in each step may be applied by any known method, but it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, JP-A-62-183460,
No. 62-183461, a method of colliding a jet of a processing liquid with the emulsion surface of a light-sensitive material, and JP-A-62-18343.
A method of increasing the stirring effect by using the rotating means of No. 61, and further moving the light-sensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. There are a method of improving the method and a method of increasing the circulation flow rate of the whole processing solution. Such a stirring improving means is effective in any of a developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, a washing solution and / or a stabilizing solution. Further, in each of the above processing liquids used in the present invention, for example, JP-A-62-183460, specification 3
The method described in the lower right column of page to the lower right column of page 4 and discharging the liquid pumped by a pump from a slit or nozzle provided facing the emulsion surface can be applied. Further, the treatment of the present invention has a relatively excellent performance in any state of the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] compared to combinations other than the present invention,
From the viewpoint of stability of liquid components, the liquid opening ratio is 0 to 0.1 cm.
^-1 is preferred. In continuous processing, practically 0.0
The range of 01 cm ^{-1 to} 0.05 cm ^-1 is preferable, and 0.002 to 0.03 cm ^-1 is more preferable.

The color light-sensitive material of the present invention generally undergoes a washing step after desilvering. A stable process may be performed instead of the water washing process. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834,
All the known methods described in JP-A-60-220345 can be used. In addition, a washing process-stabilizing process may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. For the washing and stabilizing solutions,
A water softening agent such as inorganic phosphoric acid, polyaminocarboxylic acid or organic aminophosphonic acid; a metal salt such as Mg salt, Al salt or Bi salt; a surfactant; a hardener and the like can be contained.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as the coupler), the purpose of use, the temperature of the rinsing water, the number of rinsing tanks (number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. It can be set in a wide range depending on the condition. Further, as a solution to the problems such as the propagation of bacteria and the adherence of the produced suspension to the light-sensitive material, which occurs when the amount of washing water is greatly reduced in the multi-stage countercurrent system, there is disclosed in Japanese Patent Laid-Open No.
The method of reducing calcium ion and magnesium ion described in 2-288838 can be used very effectively. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as sodium chlorinated isocyanurate described in JP-A-57-8542, and benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents"
(1986) Sankyo Publishing, edited by Hygiene Engineering Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used.

The pH of the washing water is 4-9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C.
10 seconds to 5 minutes, preferably 25 to 40 ° C. for 15 seconds to 2
A range of minutes is selected. Examples of dye stabilizers that can be used in the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. In addition, the stabilizing solution also contains a pH adjusting buffer such as boric acid or sodium hydroxide; 1
-Hydroxyethylidene-1,1-diphosphonic acid; chelating agents such as ethylenediaminetetraacetic acid; antisulfurizing agents such as alkanolamines; optical brighteners; antifungal agents and the like. The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.
In the present invention, the washing and / or stabilizing water treated with a reverse osmosis membrane can be effectively used. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate, etc. can be used.

The liquid feeding pressure in the use of these membranes is preferably ^{2 to} 10 kg / cm ² , particularly preferably ^{3 to} 7 kg / cm ² because of the stain prevention effect and the prevention of reduction of the amount of permeated water.
It is cm ² . The washing and / or stabilizing step is preferably connected in a multi-stage countercurrent system with a plurality of tanks, but it is particularly preferable to use 2 to 5 tanks.

The treatment with the reverse osmosis membrane is preferably performed on the water from the second tank for the multistage countercurrent washing and / or stabilization. Specifically, in the case of a two-tank configuration, the second tank, in the case of a three-tank configuration, the second or third tank, and in the case of a four-tank configuration, the water in the third or fourth tank is treated with a reverse osmosis membrane and permeated. Same water tank (Tank for collecting water for reverse osmosis membrane treatment; hereinafter referred to as “collection tank”)
Alternatively, it is carried out by returning to a washing and / or stabilizing tank located thereafter. Furthermore, concentrated washing and /
Alternatively, one of the measures is to return the stabilizing solution to the bleach-fixing bath upstream of the sampling tank.

A color developing agent may be incorporated in the color light-sensitive material of the present invention for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of the color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, and No. 3,342,59.
No. 9, RD magazine Nos. 14850 and 15159, Schiff base type compounds, Aldol compounds described in No. 13924, metal salt complexes described in US Pat. No. 3,719,492, JP The urethane compounds described in JP-A-53-135628 can be mentioned. The color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-64339.
No. 57-144547 and No. 58-11543.
No. 8 etc.

[0070]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. Example 1 (Production of Photosensitive Material) After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A color printing paper (101) for comparison having the following layer structure was prepared. This is used as a sample. The coating liquid was prepared as follows. Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, dye stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-1) 25
g and 180 cc of ethyl acetate, and the solution is 10%
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 cc of 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid.

On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large size emulsion A having an average grain size of 0.88 μm and small size emulsion A having a grain size of 0.70 μm (silver molar ratio), grain size distribution The coefficient of variation was 0.08 and 0.10 respectively, and each size emulsion contained 0.3 mol% of silver bromide localized on a part of the grain surface}. In this emulsion, the blue-sensitive sensitizing dyes A and B shown below were 2.0 × 10 ^-4 mol for each large-sized emulsion A and 2.0 × 10 ^-4 mol for each large-sized emulsion A per mol of silver. 2.5 × 10 ⁻⁴ mol of each is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer.

The above emulsified dispersion A and this silver chlorobromide emulsion A
And were mixed and dissolved, and a coating solution for the first layer was prepared so as to have the following composition. Preparation of Second Layer to Seventh Layer Coating Liquid The coating liquids for the second to seventh layers were also prepared in the same manner as the first layer coating liquid. The coating liquid for each layer described above was applied onto a support to prepare a sample of a light-sensitive material having a layer structure described below.

The gelatin hardener for each of the above layers is 1
-Oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-14 and Cpd-1 are provided in each layer.
Total volume 5 were added to each so that 25.0 mg / m ² and 50 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0074]

[Table 6]

[0075]

[Table 7]

[0076]

[Table 8]

1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added at 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0078]

[Chemical 6]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

[0080]

[Table 9]

[0081]

[Table 10]

[0082]

[Table 11]

[0083]

[Chemical 7]

[0084]

[Chemical 8]

[0085]

[Chemical 9]

[0086]

[Chemical 10]

[0087]

[Chemical 11]

[0088]

[Chemical 12]

[0089]

[Chemical 13]

Next, with respect to the comparative sample (101), using the coating solution A shown below, the filling rate of titanium dioxide between the support and the first layer was 80%, and the coating amounts were 4 g / m ² and 8 g.
Samples (102) and (103) coated with a titanium dioxide content of / m ² were prepared. (Coating liquid A) 400 g of a rutile titanium white pigment (Titanium White R170, Ishihara Sangyo Co., Ltd.) having an average particle size of 0.23 μm and 1.0 liter of a 10% aqueous gelatin solution were added with 4 liters of water, and 5% dodecylbenzene was used as a dispersant. 8 cc of sodium sulfonate aqueous solution was added, and ultrasonic irradiation dispersion was performed. Next, in Sample (103), the coating liquids B and C shown below were used instead of the titanium dioxide-containing layer,
Comparative Samples (104) and (105) prepared by coating a colloidal silver-containing layer containing 0.15 g / m ^{2 of} colloidal silver and a solid fine-particle dye-containing layer containing 0.10 g / m ^{2 of} solid fine-particle dye. did. However, when the colloidal silver-containing layer was coated, a hydrophilic layer using the coating liquid D described below was provided adjacent to the upper layer side of the colloidal silver-containing layer. (Coating liquid B) 2 g of anhydrous sodium carbonate was added to 1000 g of 10% gelatin aqueous solution, and the mixture was kept at 45 ° C. 10 to this
% Aqueous silver nitrate solution (500 cc) was added, and an aqueous solution containing 35 g of anhydrous sodium sulfite and 25 g of hydroquinone 1000
cc was added over 10 minutes. After the addition is complete, leave it for 10 minutes and add about 100 cc of 1N sulfuric acid to adjust the pH to 5.0.
Adjusted to. The colloidal silver sol thus obtained was poured into a cooling dish, gelled sufficiently, then cut into noodles, washed with cold water for 6 hours, and desalted to obtain a colloidal silver dispersion. (Coating liquid C) 21.7 cc of water, 3.0 cc of a 5% aqueous solution of sodium p-octylphenoxyethoxyethane sulfonate and 0.5 g of p-octylphenoxypoly (polymerization degree 10) oxyethylene ether were put in a 700 cc pot mill, 1.65 g of the dye (Dey-5) and 500 cc of zirconium oxide beads (diameter 1 mm) were added, and the mixture was dispersed for 2 hours using a vibration ball mill BO type manufactured by Central Processing Machine.

[0091]

[Chemical 14]

After the dispersion, the contents were taken out, 8.0 g of a 12.5% gelatin aqueous solution was added, and the beads were removed by filtration to obtain a solid dispersion of the dye. (Coating liquid D) 2 l of water was added to 1.0 kg of 10% gelatin aqueous solution, and 8 cc of 5% sodium dodecylbenzenesulfonate aqueous solution was added as a dispersant. With respect to the above samples (101), (102), (103), (104) and (105), the ratio of the swollen film thickness to the dry film thickness at the alkali immersion bath time of 10 seconds was 1. 7, 1.8, 1.8, 1.8 and 1.8
It was confirmed in advance. (Measurement conditions) The photosensitive material is 2 at 25 ° C and 55% humidity.
The value of the gelatin film thickness measured under the conditions after storage for at least the time was defined as the dry film thickness. Next, when the light-sensitive material was immersed in a 40 ° C. alkaline aqueous solution (0.2 mol / liter sodium hydrogen carbonate aqueous solution, which was adjusted to pH 10.0 with 0.1N sulfuric acid), the change in gelatin film thickness was observed. I asked for the progress. At this time, the gelatin film thickness at the immersion bath time of 10 seconds was defined as the swollen film thickness. After cutting the samples prepared as described above, each sample was exposed using a sensitometer (FW type manufactured by Fuji Photo Film Co., Ltd.) through gradation exposure of a three-color separation filter for sensitometry. It was The exposed sample is continuously processed (running test) using the sample (101) until the tank volume of the color developing solution is replenished using the following processing steps and color developing solution composition.
I went.

Treatment process Temperature Time Replenishment amount ^* Tank capacity (liter) Color development 40 ° C 25 seconds 73ml 2 Bleach fixing 40 ° C 20 seconds 60ml ^** 2 Rinse 35-40 ° C 15 seconds -1 Rinse 35-40 ° C 15 seconds- 1 Rinse 35-40 ℃ 15 seconds 360ml 1 Dry 80 ℃ 20 seconds (* Replenishment amount per 1 m ^{2 of} light-sensitive material) (Rins → 3 tank countercurrent method) (** In addition to the above 60 ml, rinse 120 ml was poured per 1 m ^{2 of the} light-sensitive material)

Color developing solution Tank solution Replenishing solution Water 700 ml 700 ml Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6-disulfone Acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (UVITEX CK, Ciba Geigy) 1.0 g 3.0 g sodium sulfite 0.1 g 0.1 g disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl) ) -3-Methyl-4-aminoaniline sulfate 7.0 g Added 5.0g water 1000ml 1000ml pH (25 ℃) 10.35 11.6

Bleach-fixing solution Tank solution Replenishing solution Water 600 ml 150 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 77 g 150 g Ethylenediaminetetraacetic acid 5 g 12.5 g Ammonium bromide 40 g 75 g Nitric acid ( 67%) 30g 65g Add water 1000ml 1000ml pH (25 ° C) 5.8 5.6 (with acetic acid and ammonium water) Rinse solution Ion exchange water (calcium and magnesium 3ppm or less each)

After the continuous treatment, samples (101), (10
2), (103), (104) and (105) were performed. Next, using the sample (101), continuous processing was carried out under the same conditions except that the color development time was changed to 45 seconds and the following points were changed in the above processing method.

[0097]

[Table 12]

After the continuous treatment, samples (101), (10
2), (103), (104) and (105) were performed. The reflection density of the yellow, magenta, and cyan dye images of the processed sample was measured to obtain a characteristic curve, and the maximum color density (Dmax) at that time and the minimum density (Dmin) as a measure of the degree of residual color were determined. . The result is thirteenth
Shown in the table. Then, for the purpose of obtaining the sharpness of each sample,
A rectangular pattern having a density difference of 0.5 with a spatial frequency varied deposited on a glass substrate was brought into close contact with each sample for exposure, and color development processing was performed using the above processing steps and processing solutions. The exposure was performed through a green filter so as to obtain magenta color that is most sensitive to the human eye. The developing time at this time was 15 seconds. The density of the obtained rectangular image is precisely measured with a micro densitometer and CTF is measured.
The spatial frequency with a value of 0.5 was determined and used as a measure of sharpness. The results are shown in Table 14.

[0099]

[Table 13]

[0100]

[Table 14]

As is clear from Tables 13 and 14, images obtained by ultra-rapid processing of the light-sensitive material having the titanium dioxide-containing gelatin layer of the present invention have a high Dmax especially for yellow and further have a sharpness. It turns out that is excellent in. On the other hand, a sample coated with a hydrophilic colloid layer containing a coloring substance other than titanium dioxide (10
4) and (105) are samples (102) and (10).
Although the same sharpness can be obtained as compared with 3), it can be seen that especially when the color development time is 25 seconds or less, the maximum density of yellow is low and the white background is deteriorated. Further, the sample (101) having no hydrophilic colloid colored layer is inferior in sharpness to the other samples.

Example 2 Using the sample (101) exposed in the same manner as in Example 1, continuous processing was carried out with the following processing steps and developer composition. Processing process Temperature Time Replenishment amount ^* Tank capacity Color development 40 ℃ 15 seconds 35ml 2L Bleaching fixing 40 ℃ 15 seconds 35mL 2L Rinse 40 ℃ 3 seconds -1 liter Rinse 40 ℃ 3 seconds -1 liter Rinse 40 ℃ 3 seconds -1 Liter Rinse 40 ℃ 3 seconds-1 liter Rinse 40 ℃ 6 seconds 60ml 1 liter Dry 60-80 ℃ 15 seconds * Replenishment amount per 1 m ² of light-sensitive material (5 tank counter-current method from rinse to rinse).

In the above treatment, the rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not permeate the reverse osmosis membrane was returned to the rinse for use. In addition,
In order to shorten the crossover time between the rinses, a blade was installed between the tanks and the blades were passed between them. The composition of each processing solution used for this processing is as follows.

(Color Developer) Tank Solution Replenisher Water 700 ml 700 ml Ethylenediaminetetraacetic acid 1.5 g 3.75 g Sodium triisopropylnaphthalene (β) sulfonate 0.01 g 0.01 g 1,2-dihydroxybenzene-4,6- Disulphonic acid disodium salt 0.25 g 0.7 g Triethanolamine 5.8 g 14.5 g Potassium chloride 10.0 g-Potassium bromide 0.03 g-Potassium carbonate 30.0 g 39.0 g Optical brightener (UVITEX CK, 2.5 g 5.0 g sodium sulfite 0.14 g 0.2 g disodium-N, N-bis (sulfonate ethyl) hydroxylamine 7.4 g 15.0 g 4-amino-3-methyl-N-ethyl. -N- (4-hydroxybutyl) aniline.2-p-tolu Ensulfonic acid 14.5 g 35.0 g Water was added to the above 1000 ml 1000 ml pH (25 ° C) 10.05 11.60

(Bleach-fixing solution) Tank water 600 ml Ammonium thiosulfate (70%) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (trivalent) ammonium 77 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 10 g Ethylenebisguanidine sulphate 12.0 g Acetic acid (50%) Add water to 25 ml or more 1000 ml pH (25 ° C) (Adjust with acetic acid and ammonium water) 5.5 (Replenisher has the same composition except that the pH of the tank liquid is 5.0) It is.)

(Rinse Solution) Ion-exchanged water (3 ppm or less for each of calcium and magnesium) After the completion of continuous treatment, the samples (101) and (10) of Example 1 were used.
For 2), (103), (104), and (105), after the same exposure as above, the color development time was 15 seconds, 2
Continuous processing was carried out with the same processing steps and developer composition as above except that the processing time was changed to 5 seconds and 45 seconds. The maximum color density (Dmax) of the obtained sample was obtained in the same manner as in Example 1. The results are shown in Table 15.

[0107]

[Table 15]

From Table 15, when the color developing agent of the present invention was used, particularly good results were obtained in the maximum color density of the yellow dye image as compared with the result of the sample (103) of Example 1. The minimum density and the sharpness of the image were almost the same as the results of Example 1.

Example 3 In the sample (103) of Example 1, the coating solutions B and C shown in Example 1 were used between the titanium dioxide containing layer and the first layer, and the colloidal silver containing layer and the solid A sample further provided with a fine particle dye-containing layer, (20
1) (content of colloidal silver 0.10 g / m ² ) and (2
02) (content of solid fine particle dye: 0.06 g / m ² ). However, when the colloidal silver-containing layer was coated, a hydrophilic layer using the coating liquid D was provided adjacent to the upper layer side of the colloidal silver-containing layer. Next, using the coating liquid described in Example 1, the coating amount of the colloidal silver-containing layer was 2.5 times as large as that of the sample (201) (coating amount of colloidal silver: 0.25 g / m ² ).
The comparative sample (301) having the same structure as the sample (201) except for the above (201), and the sample (202), the coating amount of the solid fine particle dye-containing layer was tripled (solid fine particle dye D
A comparative sample (302) having the same structure as the sample (202) except that the coating amount of ye-5 was changed to 0.18 g / m ² ) was prepared. Next, for the samples (201) and (202), 80 mg / m ² and 40 mg / m ^{2 of} the water-soluble dyes (Dye-3) and (Dye-4) shown in Example 1 were obtained, respectively.
Comparative samples (401) and (402) having the same structure as samples (201) and (202) except that the amount was increased to m ² were prepared. The optical reflection density value at 680 nm was obtained in advance for the above samples. Next, the above sample (201),
For (202), (301), (302), (401), and (402), the ratio of the swollen film thickness to the dry film thickness at the alkali immersion bath time of 10 seconds was 1 by the same method as in Example 1, respectively. .9, 1.9, 2.0, 2.0,
It was previously confirmed to be 1.8 and 1.9. Samples (201), (202), (301), (302),
After the same exposure for (401) and (402) as described above, a continuous development process similar to that of Example 2 was performed to obtain a color development time of 1
The treatment was carried out for 5 seconds, and the maximum color density (Dmax), the minimum density (Dmin) and the CTF value were obtained by the same method as in Example 1. The results are shown in Table 16.

[0110]

[Table 16]

From Table 16, it is found that when a light-sensitive material satisfying the constitution of the present invention is used, a white background is good even by ultra-rapid processing, and an image having more excellent sharpness is obtained without impairing the maximum color density. I understand. On the other hand, although the comparative sample can obtain the sharpness equal to or close to that of the sample of the present invention, the sufficient maximum color density is not obtained. Further, the sample (301) was not completely desilvered within the processing time of this example, and the samples (302) and (40
It was visually confirmed that 1) and (402) had deteriorated residual color.

[0112]

According to the present invention, in a color light-sensitive material obtained by ultra-rapid processing, for example, a color print, a dye image having a high sharpness, a high maximum image density, a small residual color and a good white background is obtained. It is possible to provide a color image forming method capable of obtaining a color photosensitive material, for example, a color print.

Claims (5)

[Claims] 1. A process of color development, bleaching / fixing, washing with water and / or stabilization after imagewise exposing a silver halide color photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support. In the method of forming a color image in which the white pigment is coated with a hydrophilic colloid layer having a white pigment loading of 20% by weight or more, a white pigment of ² g / m ² or more is coated on the support having the photosensitive silver halide emulsion layer. Is
A color image forming method, characterized in that a light-sensitive material containing at least one of the silver halide emulsion layers containing a silver halide emulsion having a silver chloride content of 90 mol% or more is color-developed in 5 seconds to 30 seconds. 2. A process of color development, bleaching / fixing, washing with water and / or stabilization after imagewise exposing a silver halide color photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support. In the method of forming a color image in which the white pigment is coated with a hydrophilic colloid layer having a white pigment loading of 20% by weight or more, a white pigment of ² g / m ² or more is coated on the support having the photosensitive silver halide emulsion layer. Is
Also, it has a colored layer that can be decolorized by development processing, and the light-sensitive material has an optical reflection density at a wavelength having the highest optical density in the visible light region of 400 nm to 700 nm (when not exposed).
Is 0.2 or more and 2.0 or less, and at least one of the silver halide emulsion layers has a silver chloride content of 90 mol%.
A color image forming method, which comprises color-developing a light-sensitive material containing the above silver halide emulsion in 5 to 30 seconds. 3. The film thickness of a photographic constituent layer coated on a support reaches 1.5 times or more of a dry film thickness in 30 seconds in a color developing solution. The described color image forming method. 4. The color image forming method according to claim 1, 2 or 3, wherein the developing agent used in the color developing solution is represented by the following general formula (D). [Chemical 1] 5. The processing time of the light-sensitive material is such that the bleach-fixing process is within 25 seconds and the time from the beginning of the developing process to the end of the drying process is within 120 seconds. 5. The color image forming method described in 3 or 4.