JP2604232B2 - Color photographic light-sensitive material capable of ultra-rapid processing and its color image forming method - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method thereof, and more particularly, to a high-quality color print excellent in ultra-rapid processing. The present invention relates to a novel color photographic light-sensitive material for forming a color image and a color image forming method thereof.

(Prior Art) In recent years, processing of color photographic light-sensitive materials has been increasingly required to have higher efficiency and higher productivity.
This tendency is particularly remarkable in the production of color prints, and there is a strong demand for shortening the print processing time due to demands for finishing in a short delivery period.

The process of finishing a color print consists of exposure and color development as is well known. Use of a photosensitive material with high sensitivity leads to a short circuit in the exposure time.
On the other hand, in order to shorten the color development processing time, it is essential to realize a system in which a photosensitive material capable of accelerating the development and a processing solution or a processing method are combined.

As a technique for achieving such a problem, a color photographic material containing a silver chloride emulsion instead of a silver chlorinated emulsion having a high silver bromide content, which has been widely used in photosensitive materials for color printing (hereinafter referred to as color photographic paper). Methods for processing light-sensitive materials are known. For example, International Patent Publication No. WO 87-04534 discloses a method for rapidly processing a color photographic light-sensitive material comprising a silver chloride emulsion with a color image solution containing substantially no sulfite ion and benzyl alcohol.

In addition to the above patents, JP-A-61-70552 uses a high silver chloride color photographic light-sensitive material and reduces the amount of developing solution by adding a replenishing amount that does not cause overflow to the developing bath during development. A method for replenishment is described.
No. 6655 discloses a method of processing a high silver chloride color photographic light-sensitive material with a color developing solution containing a hydroxylamine-based compound and a certain concentration or more of chloride ion for the purpose of stabilizing the processing.

As described above, by using a high silver chloride emulsion and devising the current processing solution, the conventional silver chlorobromide emulsion system can be developed for 3 minutes and 30 seconds (for example, color processing CP-20 manufactured by Fuji Photo Film Co., Ltd.). )
45 seconds phenomenon (for example, CP-40 manufactured by Fuji Photo Film Co., Ltd.)
Although the total processing time has been reduced to 4 minutes for FAS, etc., it is still hard to say that it is a satisfactory level compared to the total processing time of other color systems (for example, electrostatic transfer system, thermal transfer system, ink jet system).

For this reason, silver halide color for ultra-rapid processing has been greatly reduced by using a silver halide color development method that can produce high-quality color prints at low cost and the total processing time has been greatly reduced within 20 seconds. The development of photosensitive materials was desired.

On the other hand, rapid processing approaches other than emulsion technology are also being studied. In particular, JP-A-63-38937 discloses a technique capable of reducing the development time to 180 seconds or less in a silver chlorobromide emulsion system.
No. 63-40144, No. 63-146039, No. 61-286855, No. 6
Nos. 1-289350 and 61-286854 propose a method for controlling the swelling thickness of a light-sensitive material and the amount of gelatin applied by a processing solution, and new developing agents.

However, based on these conventional findings, it has not been possible to obtain a satisfactory high-quality color photograph with a color development time of 20 seconds or less.

(Problems to be Solved by the Invention) As is apparent from the above description, an object of the present invention is to provide a method for forming a color image with high quality and a rapid processing with a development time of 20 seconds or less. is there.

Another purpose is to greatly reduce the total processing time,
An object of the present invention is to provide a silver halide color light-sensitive material which has high image quality and can be processed even in processing time with respect to other color recording materials.

(Means for Solving the Problems) As a result of intensive studies, the present inventor has found that by controlling the "initial swelling ratio" of the photosensitive material, which is a completely new concept not found in the prior art, to 30% or more. The above objects can be effectively achieved, and a high silver chloride emulsion is used as the silver halide emulsion, and the amount of the total hydrophilic colloid used in the light-sensitive material is reduced.
The present inventors have found that it can be achieved more and more effectively by suppressing the concentration to 2.0 to 8.0 g / m ² , and arrived at the present invention. That is, the present invention is the following color photographic light-sensitive material and color image forming method.

(1) On at least one side of a support, a diffusion-resistant oil-soluble coupler that forms a dye by coupling a photosensitive silver halide emulsion and an oxidized form of an aromatic primary amine color developing agent is used. A color photographic light-sensitive material having at least two layers containing light-sensitive layers and having different light-sensitive wavelength ranges of these light-sensitive layers, characterized by having an initial swelling ratio of 30% or more, capable of ultra-rapid processing. Color photographic light-sensitive material.

(2) The photosensitive silver halide emulsion is prepared by adding 90 mol of silver chloride.
a emulsions containing more than l%, all the hydrophilic colloid, characterized in that it is a 2.0~8.0g / m ^2, item (1) super-rapid processing possible color according to use further in the light-sensitive material Photosensitive material.

(3) The ultra-rapidly processable color photographic light-sensitive material according to (2), wherein the hydrophilic colloid is gelatin and an acrylic acid-based polymer.

(4) The total gelatin (solid content) applied on the support is
3.5 to 6.5 g / m ² and the photographic component layer on the support is 1
9.3 by oxy-3,5-dichloro-s-triazine salt
Characterized in that it is hardened with the addition amount of × 10 ^-5 ~6.9 × 10 ^-4 mol / g · gelatin, claim (2) super-rapid processing possible color photographic light-sensitive material as described.

(5) A color image forming method, wherein the color photographic light-sensitive material according to (1) is color-developed within 20 seconds after imagewise exposure.

 Hereinafter, the present invention will be described in detail.

 First, the initial development behavior will be described.

Normally, the development of color photographic paper involves the process of infiltration of the developer into the film, swelling of the film of the photosensitive material, diffusion of the alkali into the film, diffusion of the developing agent into the film, and development of silver halide. Via Thereafter, there are the color development speed of the coupler and the penetration of the developing agent into the oil, but this is not a process that occurs very early in the development.

Conventional silver chlorobromide emulsion (Development time: 3 minutes 30 seconds, Fuji Photo Film Co., Ltd. color paper processing system CP-20, etc.)
In the above process, the silver halide development reaction takes place after the and have almost reached an equilibrium state. This was because the silver chlorobromide had an induction period before the development started, and the process was rate-determining. If the process is accelerated by, for example, using a silver halide emulsion of a high silver chloride type, a process which is no longer a process becomes rate-limiting. Especially when the development time is less than 20 seconds
The effect of the above process becomes very large. According to the research results of the present inventor using Fuji Color Paper Super FA and CP40FAS processing system manufactured by Fuji Photo Film Co., Ltd., it takes 15 to 20 seconds to reach the equilibrium value in the process after the start of the developing operation. It takes 5 to 6 seconds for alkali to be supplied to the bottom layer, and 7 to supply to the bottom layer in the process.
~ 8 seconds, and about 10 seconds for the lowermost layer to start developing
It turns out that it will not happen until the second.

Even if the development is performed for 20 seconds, about 10 seconds thereof are not used for the development process time.

Considering this, the above process (particularly ~)
) Is an important factor for development in less than 20 seconds. When the development reaction is sufficiently accelerated, the supply of the developing agent and the pH in the film become a rate-determining process in any case.

That is, when the developing time is about 150 seconds, the swelling thickness and the like have a large effect on the swelling thickness which has reached the equilibrium value.

In the present invention, however, the swelling in this case is intended for development in a region of a development time of 20 seconds or less. I do. Thus, the present invention is completely different from what is disclosed in the prior art.

In the present invention, the “initial swelling ratio” is calculated by the following measurement method. A few drops of a developing solution (the developing solution of Example 1) kept at 35 ° C. are dropped on the photosensitive material prepared in the present invention, and the surface of the photosensitive material is spotted once every 0.5 seconds to reduce the swelling thickness of the film. Measure. The ratio between the swelling thickness (unit: μm) and the saturated swelling thickness one second after the drop of the developing droplet is calculated, and the value is defined as the initial swelling ratio. The initial swelling ratio is a parameter of how much a developing solution can be introduced into the film at the beginning of development, and has a very large effect on rapid development which is the object of the present invention, and is a very important parameter.

The present invention is mainly intended for the development step and speeding up. However, in addition to the development step for carrying out the invention, the bleach-fixing process may be performed in the bleach-fixing process (although it is considered that the initial swelling speed is increased). It was found that removal of the main agent remaining in the layer to the bleach-fix solution was no longer possible and contributed to shortening the total processing time. Furthermore, in the rinsing step, the removal of the residual active ingredient in the rinsing liquid for the above is quick, and the residual active substance that is brought into the rinsing liquid is also small,
It has been found that there is an advantage that the amount discharged into the washing liquid is small and the amount of the washing liquid used can be reduced. When the present invention is carried out as described above, not only the speed of development but also the speed of the bleach-fixing step and the washing step can be increased, the replenishing amount of washing water can be reduced, and the size of the automatic developing machine can be reduced. I also learned that there are merits such as.

In order to increase the initial swelling ratio, which is a feature of the present invention, the following method is preferable.

First, the amount of hydrophilic colloid in the light-sensitive material layer is reduced. Since the swelling due to the hydrophilic colloid is caused by the permeation of water or alkali, the swelling is caused by gradually absorbing water from above the photosensitive layer. One second after penetrating the developing solution, water does not reach the lower part of the photosensitive layer, and as a result, the underlying emulsion layer is not developed and rapid processing cannot be performed. For this reason, the hydrophilic colloid is reduced to rapidly swell, and it becomes possible to supply the alkali and the developing agent to the lower emulsion layer.

Second, a superabsorbent polymer is added to the photosensitive layer, and part of the polymer replaces the hydrophilic colloid. In this method, not only the diffusion of the alkali and the main drug outside the membrane due to the concentration gradient,
It can be rapidly absorbed into the photosensitive layer.

Third, a hardener is used appropriately. The hydrophilic colloid is appropriately crosslinked by a hardener. Since the crosslinked portion does not absorb water, it becomes a free water passage and can promote diffusion to the lower layer. The same applies to the surface as described above, which is effective in quickly bringing water outside the system into the photosensitive layer.

In addition, it is possible to change the initial swelling behavior by adjusting the composition in the photosensitive layer or by changing the composition of the developer or the processing conditions.
The above control is an important factor. The initial swelling ratio is
40% or more is preferable for achieving the object of the present invention, and the larger the value, the more preferable.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide agent layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be performed in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having sensitivity in each wavelength region and a dye having a complementary color relationship with the light to be exposed--yellow for blue, magenta for green and cyan for red.
Incorporating a so-called color coupler for forming a color image allows color reproduction by the subtractive color method. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

As the silver halide emulsion for use in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, substantially not containing silver iodide means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the distribution of the halogen composition inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide element, and the core inside the silver halide grains and the A so-called laminated type grain having a different halogen composition from the surrounding shell (single layer or plural layers) or a structure having a non-image-like portion having a different halogen composition inside or on the surface of the grain (when the particle is on the grain surface, Particles having a structure in which portions having different compositions are joined on edges, corners, or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance.
In the case where the silver halide grains have the above-described structure, the boundary between different portions in the halogen composition may be a clear boundary or an unclear boundary due to the formation of a mixed crystal due to a composition difference. Alternatively, the structure may be positively and continuously changed.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for the light-sensitive material suitable for rapid processing of the present invention. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%, more preferably at least 95 mol%.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized layer has a layered or non-layered structure inside and / or on the surface of silver halide grains as described above.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, more preferably more than 20 mol%. These localized layers can be on the inside of the grain, on the edge, corner, or plane of the grain surface. One preferred example is a layer grown epitaxially on the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
An almost pure silver chloride emulsion having a molar ratio of 0 mol is also preferably used.

Average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is obtained by using the diameter of a circle equivalent to the projected area of the grain, and the number average is taken).
Is preferably 0.1 μm to 2 μm.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may have various crystal forms but may be a mixture. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in Chimi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7) Photographic Emulsion Chemisty by GFDuffin
(Focal Press, 1966), M by VLZelikman et al
aking and Coating Photrgraphic Emuldion (Focal Pre
ss, published in 1964). That is, any method such as an acidic method, a neutral method, and an ammonia method may be used, and the method of reacting a soluble silver salt with a soluble halide may be any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, 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 nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to a target spectral sensitivity-a spectral sensitizing dye. Examples of the spectral sensitizing dye used at this time include, for example, Heterocyclic compoun by FM Harmer.
ds-Cyanine dyes and related compounds (John Wiley
& Sons [New York, London], 1964). As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

When the present invention is applied to a color light-sensitive material, the color light-sensitive material is yellow-, magenta-, and cyan-coupled with an oxidized form of an aromatic amine-type color developing agent to form yellow, magenta, and cyan, respectively. Couplers are commonly used.

The cyan coupler, magenta coupler and yellow coupler preferably used in the present invention are represented by the following general formulas (CI), (C-II), (MI) and (MI)
(I) and (Y).

General formula (C-I) General formula (C-II) General formula (MI) General formula M-II) General formula (Y) In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentdecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

R ₁ is preferably an aryl group or a heterocyclic group in the general formula (CI), and is a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably phenyl group) of R ₇ and R ₉ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferably, Y ₃ is released at a sulfur, oxygen or nitrogen atom, and a sulfur atom released type such as described in US Pat. No. 4,351,897 or WO 88/04795 is particularly preferred.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of a bond of -Zb and a Zb-Zc bond is a double bond,
The other is a single bond. The case where the Zh-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. R ₁₀
Or to form a double or more multimers in Y _4, also Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 is advantageous in terms of low yellow side absorption and light fastness of a coloring dye. Are preferred, US Pat.
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and pyrazoloazole couplers having an alkoxy group or aryloxy group at the 6-position as described in EP-A-226,849 and EP 294,785. The use of zorotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Represents Here, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl group. Y ₅ represents a leaving group. R ₁₂ and R
₁₃ and R ₁₄ are the same as the substituents permitted for R ₁ and the leaving group Y ₅ is preferably of a type capable of leaving at either an oxygen atom or a nitrogen atom; Atomic desorption type is particularly preferred.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As a high boiling organic solvent, the following general formula (A) is preferred.
The high-boiling organic solvent represented by (E) is used.

General formula (A) General formula (B) W ₁ -COO-W ₂ General formula (C) General formula (D) Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
Homopolymers or copolymers described on the page are used, and use of an acrylamide-based polymer is particularly preferable for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 758,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. No., UK Patent No.
No. 2,066,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are described in U.S. Pat.
No. 5, JP-A-52-72224, U.S. Pat.No. 4,228,235, JP-B-52-6623, and the like, gallic acid derivatives, methylenedioxybenzenes, aminophenols are U.S. Pat.Nos. 3,457,079 and 4,332,886, respectively. In Japanese Patent Publication No. 56-21144, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,
Nos. 354,313, 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846, and JP-A-59-78344, the metal complexes are U.S. Pat. 4,241,1
55 and British Patent 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,700,455) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a compound having a second-order rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with p-anisidine. It is a compound that reacts. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition in response to a gelatin and water. On the other hand, k ₂ is slower reacting with aromatic amine developing agent remaining if Ke smaller than this range, it may not be possible to prevent the side effects of the aromatic amine developing agent remaining as a result.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R _1- (A) _n -X General formula (F II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of the chemical bonding with the residual aromatic amine-based developing agent include a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in specifications such as European Patent Publication Nos. 298321 and 277589 are preferable.

On the other hand, a compound (G) that forms a chemically inert and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development treatment is more preferably represented by the following general formula (GI) ].

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearso
n, et al., J. Am, ChemSoc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention may contain a water-soluble dye as a felter dye for a hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxinol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

Examples of hydrophilic colloids other than gelatin that can be used in the present invention include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and cellulose. Cellulose derivatives such as sulfates; sugar derivatives such as sodium alkyl acid, polydextran and starch derivatives; polyvinyl alcohol, poly-N-vinylpyrrolidone modified with polyvinyl alcohol, polyvinyl alcohol partial acetal, anionic compounds and cationic compounds , Polyacrylic acid and its neutralized product, polymethacrylic acid and its neutralized product, homopolymers such as polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. Synthetic hydrophilic polymeric substances consisting of fine each copolymer can be mentioned. In order to increase the initial swelling ratio, it is preferable to use an acrylic acid-based polymer and gelatin in combination, and as the polymer, a homopolymer or copolymer containing acrylic acid or acrylamide as a repeating unit is particularly preferable.

In addition, a hydrophilic polymer containing gelatin can be appropriately crosslinked and used to increase the initial swelling ratio.

Total hydrophilic colloid (solid content) used in the photosensitive material is 2.0
Preferably ~8.0g / m ^2, more preferably 3.5~6.5g / m ²
It is. If the amount of the hydrophilic colloid is large, development, especially the initial development is delayed, and if it is small, the physical properties of the film when wet are affected, which is not preferable. For this purpose, any of the conventionally known hardeners can be used alone or in combination.

That is, for example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylluhydantoin, etc.), dioxane derivatives (2,3-dihydroxyl) Dioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexaido-2-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (1-oxy-3,5-dichloro- S-triazine salts), mucohalogenic acids (mucochloric acid, mucophenoxycyclolic acid, etc.) and the like can be used.

Preferably used hardening agents include aldehyde compounds (eg, formaldehyde, glyoxal) and S-triazine compounds (eg, 1-oxy-3,5-dichloro-S).
-Triazine sodium salt), vinyl sulfone compounds and the like.

The amount of the hardening agent used is influenced by the presence of a hardening accelerator or a hardening inhibitor, but is preferably 1 × 10 ⁻⁶ mol / g · gelatin to 1 × 10 ⁻² mol / g · g. Used in the range of gelatin. More preferably, 5 × 10 ⁻⁵ mol / g · gelatin
5 × 10 ^-3 mol / g. Used in gelatin.

Most preferably, the total amount of gelatin used is 3.5-6.5 g /
m ² and 1-oxy-3,5-dichloro- as a hardening agent
9.3 × 10 ^{-5 to} 6.9 × 10 ^-4 mol / g depending on S-tridian salt
In this embodiment, the film is hardened with the amount of gelatin added.

Typical hardener HCHO CH ₃ CHO _{OHCCH 2 3 CHO ClCH 2 CONHCOH 2} Cl ClCH 2 COOCH 2 CH 2 OOCCH 2 Cl CH ₃ COCl CH ₃ COCH ₂ Cl CH ₂ = CHSO ₂ (CH ₂ ) ₃ SO ₂ CH = CH ₃ C (CH ₂ SO ₂ CH = CH ₂ ) _{4 CH 2 = CHCOOCOCH = CH 2 CH} 2 = CH-O-CH = CH 2 (CH ₂ = CHSO ₂ · CH ₂ CONHCH _{2 2 A} hardening aid may be used when hardening a hydrophilic colloid using these hardening agents. Examples of the hardening aid include:
Examples thereof include a hydrogen bond breaking agent such as thiourea and urea, and an aromatic hydrocarbon having a hydroxyl group such as hydroquinone.

Further, only the additive layer may be hardened by polymerizing the hardener.

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic material, or a reflective support can be used. For the purpose of the present invention, the use of a reflective support is more preferred. The "reflective support" used in the present invention is to enhance the reflectivity to sharpen the dye image formed in the silver halide emulsion layer. Such a reflective support may be made of a support coated with a hydrophobic resin dispersedly containing a light reflective material such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, or a light reflective material. Examples include those using a hydrophobic resin dispersed and contained as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Polyamide film, polymer ponate film,
There are polystyrene film, vinyl chloride resin and the like.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) of the white pigment fine particles per the specified unit area is most typically obtained by dividing the observed area into adjacent 6 || × 6 || Can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles projected on the surface of the substrate. The coefficient of variation of the occupied area ratio (%) is
Mean value of R _i () for can be determined by the ratio s / of the standard deviation s of R _i. The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing, and washing (or stabilization). Bleaching and fixing may be performed separately, instead of in a single bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferable examples are p-phenylenediamine derivatives, representatives of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is 4-amino-3-methyl-N-ethyl-N- [β-
Methanesulfonamido) ethyl] -aniline (Exemplary compound D-6).

Further, these p-phenylenediamine derivatives and salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates may be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developer.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, substantially not containing, preferably 2 ml / or less,
More preferably, the concentration of benzyl alcohol is 0.5 ml / or less, and most preferably, no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time having a function as a preservative of the developing agent, thereby reducing the dye formation efficiency. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of mol / or less, and most preferably contains no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

More preferably, the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxalic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63
-44657, 63-44656, U.S. Patent No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
No. 3749, various metals, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxyl compound described in 3,746,544 or the like may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides)
Are particularly preferred, and for details, see Japanese Patent Application No. 62-2552.
No. 70, No. 63-9713, No. 63-9714, No. 63-11300 and the like.

It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing.

Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines disclosed in Japanese Patent Application No. 63-9713. 63
Amines as described in JP-11300.

In the present invention, 3.5 × 1 chloride ion in the color developer
The content is preferably 0 ^{-2 to} 1.5 × 10 ^-1 mol / mol. Particularly preferably, it is 4 × 10 ^-2 to 1 × 10 ^-1 mol /. When the chloride ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / mol, it has a disadvantage of delaying the development, and is not preferable for achieving the object of the present invention of rapid and high maximum concentration. Further, if it is less than 3.5 × 10 ⁻² mol / mol, it is not preferable in preventing fog.

In the present invention, the bromine ion in the color developer is 3.0
× 10 ^-5 mol to 1.0 × 10 ^-3 It is preferable that the memory / contained. More preferably, it is 50 × 10 ^{-5 to} 5 × 10 ^-1 mol /. If the bromine ion concentration is higher than 1 × 10 ⁻³ mol / mol, the development is delayed, the maximum density and the sensitivity are reduced, and
If it is 0 ^-5 mol / below, it can not be sufficiently prevented fog.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When directly added to a color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, of which the preferred ones Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, bromide Thallium is mentioned, of which potassium bromide is preferable,
Sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include 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 salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate are excellent in solubility and buffering ability in a high pH region of pH 9.0 or more, and even when added to a color developing solution, they have an effect on photographic performance. It has the advantage that it has no adverse effects (such as fog) and is inexpensive, and it is particularly preferable to use these buffers.

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), tetraborate Karimou acid, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.
For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylsulfonic acid, transsiloxanediaminetetraacetic acid, 1 , 2-Diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N ' -Bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetic acid;

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat.No. 3,813,247, etc .; and JP-A Nos. 52-49829 and 50-15554. p-phenylenediamine compounds, JP-A-50-13
Quaternary ammonium salts represented by No. 7726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429.
U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796
No. 3,253,919, JP-B-41-11431, U.S. Pat.
Nos. 482,546, 2,596,926 and 3,582,346, amine compounds described in JP-B-37-16088 and JP-B-42-25201.
No. 3,128,183, JP-B-41-11431, 42
Polyalkylene oxides described in U.S. Pat. No. -23883 and U.S. Pat. No. 3,532,501, and other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be added, if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroinindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine And nitrogen-containing heterocyclic compounds such as adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1 g-4 /.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer applicable to the present invention is 20 to
The temperature is 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although the replenishment amount is preferably small, it is suitably 20 to 600 ml, preferably 50 to 300 ml, per m ^{2 of} the light-sensitive material. More preferably 60ml-200m
l, most preferably from 60 ml to 150 ml.

Next, the desilvering step applicable to the present invention will be described. As the desilvering step, generally, any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like. .

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Tetraacetic acid, propylenediaminetetraacetic acid, nitrilolic acidacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, imidic acetic acid, glycol etherdiaminetetraacetic acid and the like can be mentioned. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of a complex salt, or a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric sulfate ammonium, ferric phosphate, and the like. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc., to form a ferric ion complex salt in a solution. In addition, the cleansing agent
The iron ion complex salt may be used in excess of the iron salt complex. Among the iron complexes, iron aminopolycarboxylate is preferred,
Its addition amount is 0.01 to 1.0 mol /, preferably 0.05 to 0.5 mol.
0 mol /.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
Nos. 1,290,812, JP-A-53-95630, and compounds having a mercapto group or a disulfide bond described in Research Disclosure No. 17129 (July, 1978); -20832, 53-327
No. 35, U.S. Pat. No. 3,706,561, and the like, thiourea-based compounds or halides such as iodine and bromine ions are preferred because of their excellent bleaching power.

In addition, the bleaching solution or the bleach-fixing solution applicable to the present invention includes bromide (for example, potassium bromide, sodium bromide, ammonium bromide) or chloride (for example, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as an iodide (eg, ammonium iodide). One or more inorganic or organic acids having a pH buffering capacity, such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if necessary. And an alkali metal or ammonium salt thereof, or a corrosion inhibitor such as ammonium nitrate or guanidine can be added.

The fixing agent used in the bleach-fixing solution or the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thioate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycol Acid, thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas. These may be used alone or in combination of two or more. it can. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention,
The use of thiosulfates, especially ammonium thiosulfates, is preferred. The amount of the fixing agent per one is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleaching-fixing solutions and fixing solutions include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium sulfite, etc.), preservatives, It preferably contains a sulfite ion releasing compound such as a bisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ions
The content is preferably 0.02 to 0.05 mol / mol, more preferably 0.04 to 0.40 mol /.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed.

The amount of rinsing water in the rinsing process can vary widely depending on the characteristics of the photosensitive material (for example, the material used such as a coupler), the application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journa
l of the Society of Motion Picture and Television
Engineers), Vol. 64, pp. 248-253 (May, 1955). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 to 1 or less per 1 m ^{2 of the} photosensitive material is possible, and the effect of the present invention is remarkable. Problems occur. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, 61-12
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-A No. 145, benzotriazole described in JP-A-61-26761, copper ions and others, written by Hiroshi Horiguchi, "Bactericidal and antifungal chemistry"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) And the bactericides described in (1) and (2).

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

It is also possible to carry out the treatment with the stabilizing solution directly after the washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, for example, an aldehyde compound represented by formalin, or a film suitable for stabilizing a dye.
Examples include a buffer for adjusting the pH and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a method disclosed in
Known methods described in JP-A Nos. 8543, 58-14834, 60-220345, etc. can all be used.

In another preferred embodiment, a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid, and a magnesium or bismuth compound are used.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment.

The preferred pH of the washing step or the stabilizing step is 4 to 10, and more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably
15 seconds to 1 minute and 45 seconds, more preferably 30 seconds to 1 minute and 30 seconds.
It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like.

A specific preferable replenishing amount is 0.5 to 50 times, preferably 3 to 4 times the amount of light-sensitive material and the amount brought in from the previous bath per unit area.
It is 0 times. Alternatively, the amount is 1 or less, preferably 500 ml or less per 1 m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently.

The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water is reduced by a multi-stage countercurrent method, and is allowed to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

In the present invention, the development time for forming a color image is substantially 20 seconds or less, but it is preferable that the time of the transition (air movement) from one liquid to the next liquid is short. The transition time from the developing solution to the bleach-fixing solution and from the bleach-fixing solution to the washing solution is preferably 1/3 or less, more preferably 1/5 or less of the time in each solution.

In addition, the smaller the amount of liquid carried from each liquid to the next liquid, the better the stability of the processing liquid, and is preferably 50 cc / m ² or less. More preferably, it is 30 cc / m ² or less.

The total processing time from the start of development to the end of the drying step applied to the present invention is preferably within 1 minute and 40 seconds, more preferably within 1 minute and 30 seconds, and most preferably within 1 minute.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to this.

Example 1 The following silver halide emulsions (A) to (C) were prepared. The shapes, average grain sizes, halogen compositions and variation coefficients of the silver halide emulsions (A) to (C) are as shown below. Here, the remainder of the halogen composition is silver bromide, which is locally contained in each grain.

Silver halide emulsion of blue-sensitive silver halide emulsion layer (A)
Is a combination of a blue-sensitive sensitizing dye (Sens-1), a silver halide emulsion (B) of a green-sensitive silver halide emulsion layer is a combination of a green-sensitive sensitizing dye (Sens-2), and a red-sensitive halogen. The silver halide (C) in the silver halide emulsion layer used a red-sensitive sensitizing dye (Sens-3) and the following compounds.

(1.6 × 10 ^-4 mol per mol of silver halide) and (1.7 × 10 ^-4 mol per mol of silver halide) (4.0 × 10 ^-4 mol per mol of silver halide) and (7.8 × 10 ^-5 mol per mol of silver halide) (7.8 × 10 ⁻⁵ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer in an amount of 6.9 × 10 ⁻⁴ mol per mol of silver halide.

On a paper support laminated on both sides with polyethylene, a multilayer color photographic paper having the following layer constitution was prepared (sample 10).
1). The coating solution was prepared as follows.

First-layer coating preparation 19.1 g of yellow coupler (ExY) and color image stabilizer (Cpd
-7) 27.2 cc of ethyl acetate and solvent (Solv-
1) 8.2 g was added and dissolved, and the solution was dissolved in a 10% aqueous gelatin solution containing 8 cc of 10% sodium odesinebenzenesulfonate.
It was emulsified and dispersed to 85 cc. On the other hand, the above-described blue-sensitive sensitizing dye was added to silver chlorobromide emulsion (A) (cube, average grain size 0.90 μm, variation coefficient of grain size distribution 0.08, containing 0.6 mol% of silver bromide localized on the grain surface). One obtained by adding 1.6 × 10 ^-4 mol per mol of silver and then ^performing sulfur sensitization was prepared. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener, 0.70 g of 1-oxy-3,5-dichloro-s-triazine sodium salt
/ m ² .

The following dyes were used as irradiation prevention dyes.

The composition of each layer is shown below.

The numbers represent the coating amount (g / m ² ), and the silver halide emulsion represents the coating in terms of silver.

(Layer structure) Support Paper support laminated on both sides with polyethylene [Polyethylene on first layer contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver halide emulsion (A) 0.27 Gelatin 1.17 Yellow coupler (ExY) 0.68 Color image stabilizer (Cpd-1) 0.01 Solvent (Solv-1) 0.28 Second layer (color mixture prevention layer) Gelatin 0.63 Color mixture inhibitor (Cpd-2) 0.11 Solvent ( Solv-2) 0.28 Solvent (Solv-1) 0.27 Third layer (green sensitive layer) Silver halide emulsion (B) 0.12 Gelatin 1.25 Magenta coupler (ExY-1) 0.26 Color image stabilizer (Cpd-3) 0.079 Color image Stabilizer (Cpd-4) 0.062 Color image stabilizer (Cpd-5) 0.025 Color image stabilizer (Cpd-6) 0.0034 Solvent (Solv-2) 0.20 Solvent (Solv-3) 0.32 Fourth layer (ultraviolet absorbing layer) Gelatin 0.71 UV absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-2) 0.05 Solvent (Solv-4) 0.2 4 Fifth layer (red-sensitive layer) Silver halide emulsion (C) 0.20 Gelatin 0.89 Cyan coupler (ExC-1) 0.20 Cyan coupler (ExC-2) 0.086 Cyan coupler (ExC-3) 0.031 Color image stabilizer (Cpd- 1) 0.31 color image stabilizer (Cpd-7) 0.04 color image stabilizer (Cpd-8) 0.19 solvent (Solv-5) 0.043 sixth layer (ultraviolet absorbing layer) gelatin 0.24 ultraviolet absorber (UV-1) 0.16 solvent (Solv-4) 0.08 7th layer (protective layer) Gelatin 1.22 Acrylic-modified copolymer of polyvinyl alcohol 0.05 (degree of modification 17%) Liquid paraffin 0.02 First, a sample 101 was subjected to gradation exposure of a three-color separation filter for sensitometry using a photometer (FWH type, color temperature of light source: 3200 ° K, manufactured by Fuji Photo Film Co., Ltd.). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The exposed sample is processed using a paper processing machine.
Continuous processing (running test) was carried out until replenishment of twice the tank capacity of color development in the next processing step.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (II) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g 40 g of ammonium bromide 25 ° C) 6.0 Rinse solution (same for tank solution and replenisher) Deionized water (3ppm for calcium and magnesium respectively)
After the color development processing, the densities of yellow, magenta and cyan were measured with a densitometer to obtain a so-called characteristic curve. From these results, the difference in the exposure density (the value obtained by taking the logarithm) required to give a density of 1.0 in the 15-second processing and the 45-second processing was calculated as the sensitivity difference. The difference in exposure amount is a 15-second phenomenon, which indicates the speed of development, and is an important characteristic value for a speed-up photosensitive material.

The results obtained are shown in Example-2 together with the results of Example-2.

(Example-2) Samples 201 to 205 and Comparative Example 20A were prepared by changing only the following contents from the sample 101 of Example 1.

28% with 50% aqueous solution B-type viscometer 6r.pm About 1,000cp Table 1 shows the results of determining the initial swelling ratio of the obtained samples 201 to 205, 101 and 20A according to the method described in the specification of the present invention.

Table 2 shows the results of the same exposure and color development of Samples 201 to 205 and 20A as in Example 1, together with the results of Sample 101.

As is clear from the results in Table 2, the maximum concentrations of Samples 101 and 201 to 205 and the sufficiently low minimum concentrations of Samples 101 and 201 to 205 are lower than Comparative Example 20A, and it can be said that the objects of the present invention are achieved.
In addition, it can be understood that the sample of the present invention has a small difference in sensitivity between the development for 45 seconds and the development for 15 seconds, and the processing stability has been improved.

(Example-3) Samples 301 and 302 were prepared by modifying the sample 101 of Example-1 by the following contents.

The initial swelling ratio of Samples 301 and 302 is the same as that of Sample 101 of Example-1.
Was equivalent to

Table 3 shows the results of subjecting the samples 301 and 302 to the same exposure and color development processing as in Example-1.

It can be seen that the color development is much faster than that of Comparative Example 20A in Table 2.

(Example-4) The samples of Examples-1 and 2 were used, and among the processing steps described in Example-1, processing different from the following was performed.
The treatment agent sample numbers are 401 to 403.

The initial swelling ratio for each sample is as shown in Examples 1 to 3. Table 4 shows the measurement results of the samples 401 to 403 in the same manner as in Example-1.

Even if the developing agent is changed, the maximum density is high and the minimum density is sufficiently low, indicating that the object of the present invention has been achieved.

Further, Sample No. 101 was processed in the same manner as above, except that only the development time was 10 seconds in accordance with the above-mentioned development processing, but the highest density was high, and the lowest density was low to achieve the object of the present invention. I knew it was there.

(Effect of the Invention) According to the present invention, a high-quality color photograph can be obtained by color development within 20 seconds. In addition, since the total processing time can be reduced, ultra-rapid processing can be performed.

Claims (4)

(57) [Claims] (1) silver chloride on at least one side of a support;
A non-diffusible oil-soluble coupler which forms a cyan, magenta or yellow dye by coupling a photosensitive silver halide emulsion containing at least 90 mol% with an oxidized form of an aromatic primary amine color developing agent; In a color photographic light-sensitive material having three layers containing the same, and in which the light-sensitive wavelength ranges of these light-sensitive layers are different from each other, the total hydrophilic colloid (solid content) applied on the support is 2.0 to 8.0 g. / m ² and an "initial swelling ratio" of the photosensitive material of 30% or more. 2. An ultra-rapid processable color photographic light-sensitive material according to claim 1, wherein the hydrophilic colloid is gelatin and an acrylic acid-based polymer. 3. The total gelatin (solid content) coated on the support is 3.5 to 6.5 g / m ² and the photographic constituent layer on the support is 1-oxy-3,5-dichloro-s. 2. The color photographic photosensitive material according to claim 1, which is hardened with a triazine salt in an amount of 9.3.times.10.sup.- ^{5 to} 6.9.times.10.sup.- ⁴ mol / g. material. 4. A color image forming method, wherein the color photographic light-sensitive material according to claim 1 is color-developed within 20 seconds after imagewise exposure.