JPH09251197A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To diminish a residual color due to a spectral sensitizing dye, to relieve the load of color correction in color printing and to improve color reproducibility by incorporating a specified compd. and one of specified compds. SOLUTION: This sensitive material contains a compd. represented by formula I and one of compds. represented by formulae II, III, etc. In the formula I, each of L<1> and L<2> is -OR<1> or NR<2> R<3> (each of R<1> -R<3> is H or alkyl) and satisfies a specified condition. In the formula II, Ra1 is alkyl, cycloalykl, etc., and Ra1 is H or a group represented by Ra1 . In the formula III, X is a heterocyclic group, Rb1 is alkyl, alkenly or aryl and X and Rb1 may bond to each other to form a 5- or 7-membered ring.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. More particularly, it relates to a silver halide color photographic light-sensitive material in which residual color due to the spectral sensitizing dye after color development processing is reduced.

[0002]

2. Description of the Related Art In recent years, as a processing machine for silver halide color photographic light-sensitive materials, especially color negative light-sensitive materials (hereinafter sometimes simply referred to as color light-sensitive materials), the floor area at the installation site has been made small, A color automatic development processor called a so-called minilab, which has the advantages of small size, simple operability, easy handling of processing solutions, and drastically shortening the time from the customer's development request to return, sells color sensitive materials. It has been widely used instead of the conventional large-scale, large-scale, large-scale, centralized laboratory method in storefronts and discout stores. However, it can be said that the operability is simple and the processing solution is easy to handle, and the time and temperature in the color development process are strictly controlled by the standard, and the development process is stable and uniform to the user. It is designed so that the film can be returned. However, in the color development process that is actually carried out in minilabs including these large labs, in order to bring out special features in handling the labs, for example, we try to shorten the time from the receipt of photographed film to the return as much as possible. The processing temperature may be set higher in order to reduce the cost by increasing the number of processings per hour, or the processing solution (color developing solution or bleaching solution may be used to reduce the development processing cost per the number of processings). There is a so-called difference between laboratories in the performance of the developed film due to color development processing that deviates from the standard, such as processing with a processing solution with a large amount of accumulated fatigue solution by reducing the replenishment amount of the solution). It is the current situation. This fact is that the same subject was photographed under the same exposure conditions using the color negative film of the same production number, and color development processing was requested to laboratories at various places to perform performance evaluation, and a large amount of information was collected. It was found that there were variations in the minimum density value and the density value of the color image portion when the density was measured with cyan, magenta and yellow densities, and there was variation. More specifically, a density difference of about 0.10 was found between the minimum density of magenta and the density of the color image portion, and a density difference of about 0.04 was found between the minimum density of yellow and the density of the color image portion. Depending on the coupler used, there is almost no change in the density.Therefore, these density changes cause the spectral sensitizing dyes used in the color photosensitive material to desorb from the photosensitive material during color development processing and elute into the processing solution. This is due to the so-called residual color that remains without doing so. The problem is that films having such density changes are collected, and when printing on color paper in a mixed state, for example, excessive color correction is required for the printer each time depending on the color negative, Further, the color reproducibility of the printed color paper also fluctuates and the quality assurance is impaired, and it is strongly desired to solve this problem.

Incidentally, in order to solve the above-mentioned problem relating to the residual color, for example, US Pat. Nos. 5,188,926 and 5,19 are cited.
No. 2,646, the use of carbonamide-based or sulfoxide-based high-boiling organic solvents is described in EP 640873.
In A2, a combination of a thiacyanine type spectral sensitizing dye and a dialkylhydroquinone type compound is further disclosed in JP-A-7-19.
No. 9431 discloses a technique for reducing the residual color of the spectral sensitizing dye in the red-sensitive layer by using a 2,4-disulfonamidophenol-based compound and a diffusion-resistant amine-based compound. Is accepted. However, the latter stain by the cyanocyanine-based spectral sensitizing dye and the spectral sensitizing dye of the red-sensitive layer is mainly an increase in cyan concentration based on the aggregate of the spectral sensitizing dye,
This is intended to be reduced. On the other hand, in the stilbene compound having a triazine ring according to the present invention, similar compounds having different substituents are described in, for example, JP-A-62-25.
No. 7154 and JP-A-4-249243, these compounds are used as a fluorescent whitening agent when added to a developing solution, and their purpose of use is completely different from that of the present invention. . In JP-A-6-332127 and JP-A-6-329936, the use of the present invention and a fluorescent whitening agent similar to the present invention in a processing solution for a color paper sensitive material using a high silver chloride emulsion, the safety of the solution is described. There is a description that the residual color (color contamination) of the light-sensitive material after treatment is reduced, but these disclosed constitutions are completely different from the present invention in that they are used by being added to the treatment liquid as in the above. It is a thing. Further, it is known to use a part of the compounds represented by the general formulas (AI) to (AV) according to the present invention in the photosensitive layer. For example, U.S. Pat. Nos. 4,339,515 and 4,3.
No. 30,606 describes a light-sensitive material containing a similar compound. However, these are all for improving the image storability of the dye formed by the coupling of the coupler and the oxidized product of the color developing agent, and have different constitutions and effects from the present invention.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color photographic material in which so-called residual color after color development processing due to a spectral sensitizing dye is reduced. by this,
When the color sensitive material is a color sensitive material for photographing, it is possible to reduce the color correction of the printer at the time of color printing and bring about an effect of improving the color reproducibility of the printed positive image.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies, the inventors of the present invention have provided a silver halide color photographic light-sensitive material described below as a color photographic material capable of reducing residual color after color development processing. As a result, they have found that the object can be achieved, and completed the present invention. That is, the present invention includes (1) a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing a compound represented by the general formula (SR), A silver halide color photographic light-sensitive material containing a compound selected from the group of compounds represented by formulas (A-I) to (A-V).

[0006]

Embedded image

In the general formula [SR], L ¹ and L ² may be the same or different, --OR ¹ or --NR ² R
³ (R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group), and at least one of the following conditions is satisfied. Four substituents L ¹ and L in the general formula [SR]
² has a total of four or more substituents selected from the general formula [A] group. Four substituents L ¹ and L in the general formula [SR]
² has a total of two substituents selected from the general formula [A] group, and has a total of two or more substituents selected from the general formula [B] group.

[0008]

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In the general formula [A] group, X is a halogen atom and R is
Represents an alkyl group. In the general formulas [SR] and [A], M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium. In the general formula [B] group, R, R ′ and R ″ are hydrogen atoms or alkyl groups, and R ′ and R ″ may be connected to each other to form a ring.

[0010]

[Chemical 6]

In the general formula (AI), R _a1 is an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
A carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group;
_a2 represents a hydrogen atom or a group represented by R _a1 . However,
When R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. _Ra1 and _Ra2 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group.
X and R _b1 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-III), Y represents a nonmetallic atom group necessary for forming a 5-membered ring together with -N = C-.
Y represents a group of non-metal atoms necessary for forming a 6-membered ring together with a -N = C- group, and the terminal of Y bonded to a carbon atom of the -N = C- group is -N (R _c1 ). -, -C (R _c2 ) (R _c3 )-,
It represents a group selected from -C (R _c4 ) =, -O-, and -S- (bonded to the carbon atom of -N = C- on the left side of each group).
R _{c1 to} R _c4 represent a hydrogen atom or a substituent. In formula (A-IV), R _d1 and R _d2 may be the same or different and each represents an alkyl group or an aryl group. However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2
Is an alkyl group having 8 or more carbon atoms. General formula (AV)
Wherein R _e1 and R _e2 may be the same or different;
Each represents a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group or an aryl group. However, R _e1 and R _e2 are not simultaneously —NHR _e3 (R _e3 is an alkyl group or an aryl group). R _a1 and R _a2 , X and R
_b1 may combine with each other to form a 5- to 7-membered ring.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, the general formula [SR] will be described in more detail. In the general formula [SR], L ¹ and L ² are represented by —OR ¹ or —NR ² R ³ , and R ¹ ,
R ² and R ³ represent an alkyl group and may be the same or different. The alkyl group is a linear or branched alkyl group, and a hydrogen atom of the alkyl group may be substituted with another group. The substitutable group may be any group, but is preferably a substituent selected from the general formula [A] group and the general formula [B] group.
The alkyl group represented by R ¹ , R ² and R ³ preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The substituents in the general formula [A] group and the general formula [B] group are those generally known as hydrophilic groups. In particular, the substituents in the general formula [A] group are known as strong hydrophilic groups, so-called strongly hydrophilic groups.

In the present invention, the compound represented by the above general formula [SR] has L ¹ and L ² satisfying at least one of the above conditions. The general formula [SR] is
The two triazine rings in the molecule have symmetry by having L ¹ and L ² , respectively, and more specifically, have two rotation axes out of the plane of the molecule at the center of the molecule (center point on the double bond). It is preferable to have symmetry belonging to the C _2h point group. Here, the condition is 4 in the general formula [SR].
The condition is that one substituent L ¹ and L ² has a total of four or more substituents selected from the general formula [A] group. When the condition is satisfied, when the number of the two sulfo groups of the benzene ring constituting the stilbene in the compound of the general formula [SR] is combined, the compound has a total of six or more strongly hydrophilic groups in the molecule. Equivalent to. Here, the number of substituents selected from the general formula [A] group is preferably an even number, and the number is preferably 8 or less, more preferably 6 or less. As described above, if the number of the above-mentioned substituents is too large or too small, the effect of preventing residual color is lowered, which is not preferable. The conditions are that the four substituents L ¹ and L ² in the general formula [SR] are a total of two substituents selected from the group [A] and a total of two or more substituents selected from the general formula [B] group. It is a condition having a group. When the conditions are satisfied, the compound represented by the general formula [SR], when combined with the number of two sulfo groups of the benzene ring constituting stilbene, has a total of four strongly hydrophilic groups and a total of two or more hydrophilic groups in the molecule. It is equivalent to having a functional group. Here, the number of substituents selected from the general formula [B] group is preferably an even number, and the number is preferably 10 or less, more preferably 4 or less. As described above, if the number of the above-mentioned substituents is too large or too small, the effect of preventing residual color is lowered, which is not preferable. Among the compounds represented by the above general formula [SR] related to the present invention, more preferable compounds are the above-mentioned conditions or
It satisfies the conditions.

The compound represented by the above-mentioned general formula [SR] having a strongly hydrophilic group under the above-mentioned conditions or has a structure generally known as a stilbene-based optical brightening agent.
However, for example, (I-30) and (I-31) described in JP-A-62-257154,
Conventional optical brighteners having a total of four or more strongly hydrophilic substituents in the molecule, such as the compound described in No. 9243 (Comparative-1), usually have two triazine rings in the molecule having an anilino group. There was a feature to have. Further, even with a conventional stilbene fluorescent brightener having a triazine ring having no anilino group, a specific compound satisfying any of the above conditions has not been known. The stilbene-based optical brightener represented by the general formula [SR], which satisfies the above-mentioned condition or any one of the present invention, has a triazine ring having a substituent L ¹
And L ² are characterized by not having an anilino group but having a strongly hydrophilic group and having a symmetrical structure as described above, which is different from the fluorescent whitening agent described in JP-A-4-249243.

In the compound of the general formula [SR] in the present invention, the substituents L ¹ and L ² have the characteristics as described above, and specific examples of L ¹ and L ² are methoxy group, ethoxy group and propoxy group. Group, isopropoxy group, butoxy group, isobutoxy group, pentyloxy group, hexyloxy group, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group,
Isobutylamino group, 2-hydroxyethoxy group, 3-
Hydroxypropoxy group, 4-hydroxybutoxy group,
2-hydroxyethylamino group, 3-hydroxypropylamino group, 4-hydroxybutylamino group, 2-hydroxyethylethylamino group, 3-hydroxypropylpropylamino group, 4-hydroxybutylbutylamino group, dimethylamino group, diethylamino Group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, di2-hydroxyethylamino group, di3-hydroxypropylamino group, dihydroxybutylamino group, 2-sulfoethoxy group, 3-sulfopropoxy group Group, 4-sulfobutoxy group, 2-sulfoethylamino group, 3-sulfopropylamino group, 4-sulfobutylamino group, di2-sulfoethylamino group, di3
-Sulfopropylamino group, di4-sulfobutylamino group, 2-sulfoethylmethylamino group, 3-sulfopropylmethylamino group, 4-sulfobutylmethylamino group, 2-sulfoethylethylamino group, 3-sulfopropyl Ethylamino group, 4-sulfobutylethylamino group, 2-carboxyethoxy group, 3-carboxypropoxy group, 4-carboxybutoxy group, 2-carboxyethylamino group, 3-carboxypropylamino group, 4-
Carboxybutylamino group, di2-carboxyethylamino group, di3-carboxypropylamino group, di4-carboxybutylamino group, 2-carboxyethylmethylamino group, 3-carboxypropylmethylamino group, 4
-Carboxycarboxymethylamino group, 2-carboxyethylethylamino group, 3-carboxypropylethylamino group, 4-carboxybutylethylamino group, 2-sulfoethoxy group, 3-sulfoxypropoxy group, 4-sulfoxybutoxy group A 2-sulfoxyethylamino group,
3-sulfoxypropylamino group, 4-sulfoxybutylamino group, di2-sulfoxyethylamino group, di3-
Sulfoxypropylamino group, di4-sulfoxybutylamino group, 2-sulfoxyethylmethylamino group, 3-
Sulfoxypropylmethylamino group, 4-sulfoxybutylmethylamino group, 2-sulfoxyethylethylamino group, 3-sulfoxypropylethylamino group, 4-sulfoxybutylethylamino group, trimethylammoniomethylamino group, Examples thereof include a trimethylammonioethylamino group, a trimethylammoniopropylamino group, a triethylammoniomethylamino group, a triethylammonioethylamino group and a triethylammoniopropylamino group. More preferably, methoxy group, ethoxy group, 2-hydroxyethoxy group, 2-hydroxyethylamino group, 2-sulfoethylamino group, di2-sulfoethylamino group, 2-carboxyethylamino group, di2-carboxyethyl group. Examples thereof include an amino group and a di2-hydroxyethylamino group.

The preferable hydrophilicity of the compound represented by the general formula [SR] in the present invention is that the logP value is -30 or more and -4.
And more preferably -18 or more and -7 or less. Here, the logP value represents a value defined by a logarithmic value of a distribution ratio P (= [concentration in octanol] / [concentration in water]) of the compound in a binary system of octanol / water. If the logP value is -4 or more, it is difficult to elute from the light-sensitive material film into the processing solution, and the improvement in residual color is reduced. Is not preferred because it becomes smaller. Further, the compound of the general formula [SR] in the present invention desirably has a large diffusion coefficient in a gelatin film under various processing conditions. For example, if the diffusion coefficient in an aqueous solution of pH 5 is 1.0
It is preferably at least × 10 ⁻⁸ cm ² / sec, more preferably at least 2.0 × 10 ⁻⁸ cm ² / sec. In an aqueous solution of pH 10,
2.0 × 10 ^-8 cm ² / sec or more is preferable, 5.0 × 10 ^-8 cm ² / se
c or more is more preferable. The diffusion coefficient can be measured by monitoring with a spectrophotometer how the optical brightener molecules in the optical brightener aqueous solution permeate and diffuse into the adjacent water across the gelatin film. Journal of Po
lymer Science, Vol. 30, 2075 (1985). Specific examples of the diaminostilbene-based fluorescent brightener of the general formula [SR] used in the present invention include those in which L ¹ and L ² are represented by the following atomic groups. Is not limited to these.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

The compound of the general formula [SR] can be synthesized by a conventionally known method. For example, 4,4'-
Sodium 4,4'-bistriazinylaminostilbene-2,2'-disulfonate is synthesized by condensing sodium diaminostilbene-2,2'-disulfonate with cyanuric chloride, and then condensing alcohols or amines. Can be synthesized. Specifically, it can be synthesized by the following method. The synthesis example of the optical brightener is shown below. Synthesis of Compound (SR-13) 10.2 g of cyanuric chloride was dissolved in 100 ml of acetone, and 100 g of a 10% aqueous solution of sodium diaminostilbendisulfonate was added dropwise over 20 minutes while cooling with ice. During this time, the pH of the reaction solution was adjusted to 5 with an aqueous sodium carbonate solution.
~ 7. After stirring was continued for another 30 minutes, 100 g of an 18% aqueous solution of taurine was added. Thereafter, acetone was distilled off by heating, and the mixture was stirred at an internal temperature of 95 ° C for 3 hours.
During this time, the pH of the reaction solution was maintained at 6 or more with an aqueous sodium carbonate solution. After the completion of the reaction, the mixture was cooled and salted out to give pale yellow crystals 1
2 g was obtained. It has a mass spectrum and NMR
And it was confirmed to be Compound (SR-13). λ max = 348 nm (ε = 4.65 × 10 ⁴ , H ₂ O)

Synthesis of Compound (SR-25) 10.2 g of cyanuric chloride was dissolved in 100 ml of acetone, and 100 g of a 10% aqueous solution of sodium diaminostilbendisulfonate was added dropwise over 20 minutes while cooling with ice. During this time, the pH of the reaction solution was adjusted to 5 with an aqueous sodium carbonate solution.
~ 7. After stirring for another 30 minutes, the internal temperature was reduced to 4
The temperature was raised to 0 ° C. and 35 g of an 18% aqueous solution of taurine was added.
After heating for 1 hour, acetone was distilled off, 50 g of a 20% aqueous solution of N-methyltaurine was added, and the mixture was stirred at an internal temperature of 95 ° C. for 3 hours. During this time, the pH of the reaction solution was maintained at 6 or more with an aqueous sodium carbonate solution. After completion of the reaction, the mixture was cooled and salted out to obtain 8.3 g of pale yellow crystals. It was confirmed from the mass spectrum and NMR that this compound was the compound (SR-25). λ max = 345 nm (ε = 4.38 × 10 ⁴ , H ₂ O) Further, other compounds and comparative compounds can be easily synthesized by the same method as above. Industrial Chemistry Magazine Vol. 60 No. 5 P. 604 (1957).

The compound of the general formula [SR] is effective both when used alone and when used in combination with a plurality of other diaminostilbene compounds. A compound of [SR],
Alternatively, a diaminostilbene compound represented by the following general formula [SR-c] is preferable.

[0025]

Embedded image

In the general formula [SR-c], L ³ , L ⁴ ,
L ^5, and L ⁶ are represented by -OR ⁸ or -NR ⁹ R ^10, it may be the same or different, respectively. Here, R ⁸ , R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group or an alkyl group having a substituent. General formula [SR-
Specific examples of the compound represented by c) include the compounds in Table 6.

[0027]

[Table 6]

As the fluorescent whitening agent which can be used in combination with the compound of the general formula [SR], a commercially available diaminostilbene type fluorescent whitening agent may be used. Examples of commercially available compounds include, for example, Dyeing Note, 19th Edition (Syokusha) 165-P. 168
And among the products listed here
Whitex RP or Whitex BRF liq. Is preferred. The coating amount of the compound represented by the general formula [SR] of the present invention is in the range of 0.1 to 100 mol per mol of the sensitizing dye with respect to the coating amount of all the sensitizing dyes used in the color light-sensitive material. is there. It is preferably in the range of 1 to 50 mol, and more preferably in the range of 2 to 30 mol. The compound of the general formula [SR] may be used alone or in combination of two or more kinds.

In the present invention, when the density of yellow, magenta and cyan after the color development processing is measured as described above, it is about 0.04 in the yellow color image portion and about 0.10 in the magenta color image portion. The density fluctuation is observed, and the density fluctuation is not observed in the cyan color image portion, and it is intended to improve the density fluctuations of yellow and magenta. As a result of analysis, it was revealed that the spectral sensitizing dye used in each color-sensitive layer was the main cause of this density fluctuation. The sensitizing dye was used at the stage when color development processing was completed. It is intended to prevent it from remaining in the film. Although the reason for this residual color is not clear yet by using the compound represented by the general formula [SR] of the present invention,
It has been found that it can be reduced. Further, the fluctuations in the yellow and magenta densities are due to the sensitizing dyes used in the green-sensitive layer and the red-sensitive layer,
This residual color is not due to the sensitizing dye aggregates,
It is becoming clear that the main factor is the residual color caused by remaining as a monomer. In addition,
The above-mentioned yellow and magenta color image areas mean the entire density range from the minimum density (fog) area to the maximum density.

The additive layer of the compound represented by the general formula [SR] of the present invention used for reducing this concentration fluctuation may be a photosensitive layer or a non-photosensitive layer. It is preferable that 1/2 or more of the total amount used is used in a non-photosensitive manner, and the amount used in the photosensitive layer is small. This is to avoid the influence on the photographic property as much as possible. The non-photosensitive layer is, for example,
An antihalation layer, an intermediate layer, a yellow filter layer, a protective layer and the like. Further, the general formula [SR] of the present invention
Like the sensitizing dye, it is preferable that the compound represented by the formula (1) does not remain in the photosensitive material after color development processing. This is because the compound has an optical brightening effect, and the coupler gives a somewhat lower concentration even if the amount of dye produced by the coupling reaction is the same.

The method of adding the compound of the general formula [SR] is not particularly limited. It may be added as an aqueous solution immediately before coating, or may be added as a mixture with an aqueous solution of other additives. When it is used in the photosensitive layer, it may be added during or immediately after the preparation of the silver halide emulsion.
Further, colloidal silver or non-photosensitive fine grain silver halide added in advance may be used.

Next, the compounds represented by formulas (AI) to (AV) will be described in more detail. The alkyl group referred to in the present invention is a linear, branched, or cyclic alkyl group, and may have a substituent. In the general formula (AI), _Ra1 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl,
t-octyl, decyl, dodecyl, hexadecyl, benzyl), cycloalkyl group (preferably having 6 to 40 carbon atoms)
Is a cycloalkyl group such as cyclohexyl), an alkenyl group (preferably an alkenyl group having 2 to 36 carbon atoms such as allyl, 2-butenyl, isopropenyl, oleyl, vinyl), a cycloalkenyl group (preferably having 6 to 40 carbon atoms). Is a cycloalkenyl group of, for example, cyclohexenyl), an aryl group (preferably an aryl group of 6 to 40 carbon atoms such as phenyl and naphthyl), an acyl group (preferably an acyl group of 2 to 36 carbon atoms such as acetyl, benzoyl, pivaloyl). , Α- (2,4-di-tert-amylphenoxy) butyryl, (3-cyclohexen-1-yl) carbonyl, (3-cyclohexan-1-yl) carbonyl, myristoyl, stearoyl, naphthoyl,
m-pentadecylbenzoyl, (5-norbornene-2
-Yl) canbonyl (5-norbornan-2-yl) canbonyl, isonicotinoyl), an alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 36 carbon atoms, such as methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl). ), An alkyl or arylsulfinyl group (preferably an alkyl or arylsulfinyl group having 1 to 40 carbon atoms such as methanesulfinyl and benzenesulfinyl), a carbamoyl group (including an N-substituted carbamoyl group, preferably 1 to 40 carbon atoms). A carbamoyl group of N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-
N-phenylcarbamoyl), sulfamoyl group (N-
It also contains a substituted sulfamoyl group, preferably having 1 to 1 carbon atoms.
40 sulfamoyl groups such as N-methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl ), An alkoxycarbonyl group (preferably having 2 to 2 carbon atoms).
36 alkoxycarbonyl groups such as methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 7 to 40 carbon atoms, such as phenoxycarbonyl). , Naphthoxycarbonyl). R _a2 represents a hydrogen atom or the group represented by R _a1 .

In the general formula (A-II), a heterocyclic group (a group forming a 5- to 7-membered hetero ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom or a phosphorus atom as a ring-constituting atom) The bonding position of the heterocycle (position of the monovalent group) is preferably a carbon atom, for example, 1,
3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, prenyl, quinolyl, imidazolyl, 1,
2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl). R _b1 has the general formula (A-
It represents an alkyl group, alkenyl group or aryl group having the same meaning as R _{a1 in} I).

In the general formula (A-III), Y is -N = C.
-A non-metallic atom group necessary to form a 5-membered ring together with (for example, the ring group formed is imidazolyl, benzimidazolyl, 1,3-thiazol-2-yl, 2-imidazolin-2-yl, purinyl, 3H -Indol-2-yl). Y is a group of nonmetallic atoms necessary for forming a 6-membered ring together with the -N = C- group, and -N
The end of Y bonded to the carbon atom of the ═C-group is -N (R _C1 )-, -C
(R _C2 ) (R _C3 )-, —C (R _C4 ) =, —O—, a group selected from —S— (bonded to the carbon atom of —N═C— on the left side of each group) Represents R _{c1 to} R _c4 may be the same or different,
Represents a hydrogen atom or a substituent (eg, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a halogen atom). Here, the alkyl group, the alkenyl group, and the aryl group are represented by the general formula (A-
It has the same meaning as the alkyl group, alkenyl group and aryl group in R _a1 of I), and the alkoxy group, the alkylthio group, the alkyl group of the alkylamino group and the aryloxy group, the arylthio group and the aryl group of the arylamino group also have the general formula ( It has the same meaning as described in R _a1 of AI). Halogen atom is, for example, chlorine, bromine,
Represents a fluorine atom. Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl,
Quinoxalinyl, 6H-1,2,5-thiadiazine-6
-Ill.

In the general formula (A-IV), R _d1 and R _d
d2 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms, for example, methyl, ethyl, i-propyl, cyclopropyl, n-butyl, isobutyl, hexyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl ) Or an aryl group (preferably having 6 carbon atoms)
-40 aryl groups, for example, phenyl, naphthyl). However, when R _d1 and R _d2 are simultaneously an unsubstituted alkyl group and R _d1 and R _d2 are the same group, R _d1 and R _d2 are an alkyl group having 8 or more carbon atoms.

In the general formula (A-V), R _e1 and R _e
e2 is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group (preferably an alkylamino group having 1 to 50 carbon atoms, such as methylamino, ethylamino, diethylamino, methylethylamino, propylamino, dibutylamino, cyclohexyl Amino, t-octylamino, dodecylamino, hexadecylamino,
Benzylamino, benzylbutylamino), an arylamino group (preferably an arylamino group having 6 to 50 carbon atoms such as phenylamino, phenylmethylamino, diphenylamino, naphthylamino), and an alkoxy group (preferably having 1 to 36 carbon atoms) For example, methoxy, ethoxy, butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyloxy, tridecyloxy, hexadecyloxy), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms) For example, phenoxy, naphthoxy), an alkylthio group (preferably an alkylthio group having 1 to 36 carbon atoms, for example, methylthio, ethylthio, i-propylthio, butylthio,
Cyclohexylthio, benzylthio, t-octylthio, dodecylthio), an arylthio group (preferably an arylthio group having 6 to 40 carbon atoms, for example, phenylthio,
Naphthylthio), an alkyl group (preferably having 1 to 3 carbon atoms)
6 alkyl groups such as methyl, ethyl, propyl,
Butyl, cyclohexyl, i-amyl, sec-hexyl, t-octyl, dodecyl, hexadecyl), and an aryl group (preferably an aryl group having 6 to 40 carbon atoms, such as phenyl and naphthyl). Where _Re1 and _Re2
Are not simultaneously -NHR (R is an alkyl group or an aryl group).

R _a1 and R _a2 , X and R _b1 are bonded to each other to form 5
A 7-membered ring, for example, a succinimide ring,
Examples thereof include a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring. Each group of the compounds represented by the general formulas (AI) to (AV) may be further substituted with a substituent.
Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group,
Alkylamino group, arylamino group, carbamoyl group, sulfamoyl group, sulfo group (salt thereof), carboxyl group (salt thereof), halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl Group, acyloxy group, hydroxyamino group, quaternary ammonio group, phosphoric acid residue, phosphorous acid residue, group having a polyether structure containing at least 3 oxygen atoms, containing at least 3 nitrogen atoms Examples include groups having a polyamine structure.

In the general formula (AI), R _a2 is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R _a1 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group or a carbamoyl group. , Sulfamoyl group, alkoxycarbonyl group,
It is preferably an aryloxycarbonyl group, more preferably R _a2 is an alkyl group or an alkenyl group, and R _a1 is an acyl group, an alkyl or arylsulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or aryloxy. A compound that is a carbonyl group. Most preferably, R _a2 is an alkyl group and R _a1 is an acyl group.

In the general formula (A-II), R _b1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-II-1).

[0040]

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[0041] In formula (A-II-1), R b1 represents R _b1 of the general formula (A-II), a non-metallic atomic group necessary for X ₁ to form a 5- or 6-membered ring Represent. The general formula (A-
Among the compounds represented by II-1), the case where X ₁ forms a 5- to 6-membered heteroaromatic ring is more preferred. Furthermore, the compound represented by the following general formula (A-II-2) is most preferable.

[0042]

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[0043] In formula (A-II-2), R b1 represents a R _b1 in formula (A-II). R _b2 and R _b3 may be the same or different and each represent a hydrogen atom or a substituent. Among the compounds represented by the general formula (A-II-2), R _b2 and R _b3 are each a hydroxyamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, Particularly preferred is an arylthio group, an alkyl group or an aryl group.

Of the compounds represented by the general formula (A-III), it is preferable that Y is a group of non-metal atoms necessary for forming a 5-membered ring, and it is bonded to the carbon atom of the -N = C- group. It is more preferable that the terminal atom of Y is a nitrogen atom. Y
Most preferably forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring.

Of the compounds represented by formula (A-IV), those in which R _d1 and R _d2 are alkyl groups are preferable. On the other hand, in the general formula ( _AV ), R _e1 and R _e2 are preferably a group selected from a hydroxyamino group, an alkylamino group and an alkoxy group. Particularly preferably, R _e1 is a hydroxylamino group and R _e2 is an alkylamino group.

Of the compounds represented by the general formulas (AI) to (AV), compounds having a total carbon number of 15 or less are preferable in that they act on layers other than the additive layer, and vice versa. A compound having a total carbon number of 16 or more is preferable for the purpose of acting only on the additive layer. General formula (AI)-(A-
V) among the compounds represented by the general formula (AI),
Those represented by (A-II), (A-IV) and (A-V) are preferable, more preferably general formulas (A-I) and (A-).
IV) and (A-V), more preferably those represented by the general formulas (AI) and (A-V). The general formulas (A-I) to (A-V) of the present invention are shown below.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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These compounds of the present invention are commercially available from J. Org. Che.
m., 27, 4054 ('62), J. Amer. Chem. Soc., 73,2981 ('5
1), it can be easily synthesized by the method described in JP-B-49-10692 or the like or a method analogous thereto.

The coating amount of the compounds represented by the general formulas (AI) to (AV) of the present invention is 1 to 300 mg per 1 m ^{2 of the} light-sensitive material.
It is. It is preferably 2-200 mg, 5-150 mg
Is more preferable. These compounds are used for at least one layer constituting the color light-sensitive material, but the same compound may be used for a plurality of layers, or different compounds may be used for a plurality of layers. Furthermore, a plurality of compounds may be used in the same layer, and for example, a water-soluble compound and an oil-soluble compound may be used in the same layer. Any water-soluble compound can be used in any layer constituting the color light-sensitive material. In the case of an oil-soluble compound, it is preferably used in the photosensitive layer. When using these compounds,
It may be dissolved in water or a water-soluble organic solvent such as methanol or DMF, or a mixed solvent thereof, or may be dissolved in a high-boiling point organic solvent and added as an emulsified dispersion.
The timing of addition may be either during coating or during emulsion preparation.

The compounds represented by the general formulas (A-I) to (A-V) of the present invention are the same as the compounds represented by the above general formula [SR], the residual color after the color development processing of the sensitizing dye. It shows the effect of reducing The effect of reducing the residual color is, for example, that the residual color is increased by a coupler having a phenolic group or a hydrogen bond donor group in European Patent No. 546500A1. Therefore, the compound of the present invention acts as a hydrogen bond acceptor or an electron donor. However, it is considered that the bond between the sensitizing dye after the color development processing and the above-mentioned coupler is cleaved without disturbing the bond between the sensitizing dye and the silver halide to facilitate desorption.

Further, in the present invention, the above general formula [S
R], a compound represented by the above general formula (AI)
Both the compounds represented by (A-V) reduce the residual color of the sensitizing dye, but the reduction of the residual color by the combined use of these compounds further increases the action and effect and shows an excellent improvement. Is.

The general formulas (AI) to (A- of the present invention
The compound represented by V) is disclosed as a compound for improving the storability of the color light-sensitive material as described above. Has a purpose of use, and the effect is remarkably exhibited, and the problem to be solved obviously is completely different. However, the effect of improving the storability of the light-sensitive material with time can be recognized even if the method of using the compound is different.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH And so on. Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL starts from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8, as described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448 and 63-89850, are described.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as RL is disposed adjacent to or close to the main photosensitive layer.

The preferred silver halide for use in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than about 30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid.
307105 (Nov. 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glaf).
kides, Chimie et Phisique Photographiques, Paul Mo
ntel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion C
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-21.
4852, a silver halide grain in which the inside of the grain is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition.
As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
Particularly, the thickness is preferably 0.05 to 0.6 μm. The grains may be regular grains or polydispersed emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains).
% Having a particle diameter within ± 40% of the average particle diameter).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257 (A-4
] -63 (p.134), (A-4) -73, -75 (p.139); EP486,965
M-4, -6 (page 26), M-7 (page 27); EP 571,959A M-45 (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), the compound of formula (1) of EP 568,037A (especially (23) (page 11)), and the compounds of formulas (I), (II), Compounds represented by (III) (especially I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

The following additives are preferable as additives other than the coupler. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69-118
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29 SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII),
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The above-mentioned color photosensitive material for photographing is preferable. It also includes those for lens-equipped film units described in JP-B-2-32615 and JP-B-3-39784. Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, RD. ing. Preferred are polyester-based supports. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
T _1/2 is the time until the film thickness reaches 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. It is defined as The film thickness is
Means the film thickness measured at 25 ° C and 55% relative humidity (2 days), and T _1/2 is Photographic Science and Engineering of A. Green et al.
(Photogr.Sci.Eng.), 19 square, 2, 124 to 129 can be measured by using a swellometer (swelling meter) of the type. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling ratio is 1
50-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ It can be calculated by the film thickness. The light-sensitive material of the present invention comprises a magnetic recording layer, an antistatic layer, a sliding layer, an intermediate layer, a protective layer and the like on the side opposite to the side having the emulsion layer, and the total dry film thickness is 2 μm.
It is preferable to provide a back layer having a thickness of m to 20 μm. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention has the above-mentioned RD. No. 1764.
No. 18716, No. 18716, 651 left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development. Next, the processing solution for the color negative film used in the present invention will be described.
The compounds described in JP-A-4-121739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used in the color developing solution used in the present invention. As a color developing agent for particularly rapid processing, 2-methyl-4- [N-ethyl-
N- (2-hydroxyethyl) amino] aniline, 2-
Methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred. These color developing agents are preferably used in the range of 0.01 to 0.08 mol per liter of color developing solution,
Particularly, it is preferably used in the range of 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol. The replenisher for the color developing solution preferably contains 1.1 to 3 times the concentration of the color developing agent, and particularly preferably 1.3 to 2.5 times the concentration.

Hydroxylamine can be widely used as a preservative for the color developing solution, but when higher preservability is required, substitution of an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl). Hydroxylamine is preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine. The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, and further preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution). The color developer contains
Sulfite is used as an anti-talling agent for oxides of color developing agents. The sulfite is preferably used in an amount of 0.01 to 0.05 mol, and particularly preferably 0.02 to 0.04 mol, per liter. In the replenisher, these 1.1 ~
It is preferable to use it at a concentration of 3 times. Further, the pH of the color developing solution is preferably in the range of 9.8 to 11.0, but particularly 10.0
˜10.5 is preferable, and in the replenisher, it is preferable to set a high value in the range of 0.1 to 1.0 from these values. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used.

The replenishing amount of the color developing solution is preferably 80 to 1300 ml per 1 m ² of the light-sensitive material, but it is preferably smaller from the viewpoint of reducing the environmental pollution load, specifically 80 to 6
It is preferably 00 ml, more preferably 80 to 400 ml. The bromide ion concentration in the color developing solution is usually 0.01 to 1 liter / liter.
Although it is 0.06 mol, it is preferably set to 0.015 to 0.03 mol per liter for the purpose of suppressing the fog while maintaining the sensitivity, improving the discrimination, and improving the graininess. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions. C = A-W / V C: Bromide ion concentration in the color developing replenisher (mol / liter) A: Target bromide ion concentration in the color developing solution (mol / liter) W: 1m ² of light-sensitive material is colored Amount of bromide ion eluted from the light-sensitive material to the color-developing solution when developed (mol) V: Replenishment amount of color-development replenisher for a light-sensitive material of 1 m ² (liter). When the bromide ion concentration is set, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2 can be used as a method for increasing the sensitivity.
It is also preferable to use a development accelerator such as pyrazolidones represented by -hydroxymethyl-3-pyrazolidone and thioether compounds represented by 3,6-dithia-1,8-octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having a bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include JP-A-5-72694 and JP-A-5-7333.
The compounds described in No. 12 are preferred, and 1,3-diaminopropanetetraacetic acid, particularly, a ferric complex salt of the compound of Specific Example 1 on page 7 of JP-A-5-73312 is preferred. In addition, in order to improve the biodegradability of the bleaching agent, JP-A-4-218845, 4-268552, EP588,
289, 591,934, and the compound ferric complex salts described in JP-A-6-208213 are preferably used as a bleaching agent. The concentration of these bleaching agents is 0.05 per liter of bleaching solution.
The amount is preferably from 0.3 to 0.3 mol, and particularly from the viewpoint of reducing the amount discharged to the environment, it is preferably designed from 0.1 to 0.15 mol. Further, when the bleaching solution is a bleaching solution, it is preferable to contain 0.2 mol to 1 mol of bromide per liter, particularly 0.3 to 0.8 mol. The replenisher for the bleaching solution basically contains the concentrations of the respective components calculated by the following formula. This allows
The concentration in the mother liquor can be kept constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (treatment tank liquid) C _P : Consumed during treatment Concentration of components V ₁ : Replenishing amount of replenisher having bleaching ability for 1 m ² of light-sensitive material (mL) V ₂ : Bring-in amount of 1 m ² of light-sensitive material from the previous bath (mL) It is preferable to contain an agent, and it is particularly preferable to contain a dicarboxylic acid having a low odor such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. Also, JP-A-53-95630, RDN
It is also preferable to use known bleaching accelerators described in O. 17129, US 3,893,858. The bleaching solution is preferably replenished with 50 to 1000 ml of the bleach replenishing solution per 1 m ² of the light-sensitive material, particularly 80 to 500 ml, more preferably 100 to 300 ml. Further, it is preferable to perform aeration on the bleaching solution.

Regarding the processing liquid having fixing ability, Japanese Patent Application Laid-Open No.
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied. In particular, in order to improve the fixing speed and the homeostasis, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having fixing ability. It is preferable. In addition to the p-toluenesulfinic acid salt, the sulfinic acid described in JP-A 1-224762 can also be used.
It is preferable from the viewpoint of improving the homeostasis. It is preferable to use ammonium as a cation in a solution having a bleaching ability and a solution having a fixing ability from the viewpoint of improving desilvering ability, but from the viewpoint of reducing environmental pollution, it is preferable to reduce or eliminate ammonium. . In the bleaching, bleach-fixing and fixing steps, jet stirring described in JP-A-1-309059 is particularly preferable. The replenishing amount of the replenisher in the bleach-fixing or fixing step is 100 to 1000 ml, preferably 150 to 700 ml, and particularly preferably 200, per 1 m ² of the light-sensitive material.
~ 600 ml. In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher. The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is cascade-piped to form a multistage countercurrent system. Generally, the two-tank cascade configuration is efficient because of the balance with the size of the developing machine.
The ratio of the processing time in the front tank and the rear tank is
The range of 0.5: 1 to 1: 0.5 is preferable, and the range of 0.8: 1 to 1: 0.8 is particularly preferable. In the bleach-fixing solution or the fixing solution, it is preferable to allow a free chelating agent which is not a metal complex to be present from the viewpoint of improving the preservative property. It is preferred to use chelating agents.

Regarding the washing and stabilizing steps, JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16
The contents described in the line can be preferably applied. In particular, EP 504,60 replaces formaldehyde in stabilizers.
9. Use of the azolylmethylamines described in 519,190 and N-methylolazoles described in JP-A-4-362943, and the use of an interface free of image stabilizers such as formaldehyde by dimerizing a magenta coupler. It is preferable to use a liquid of the activator from the viewpoint of preserving the working environment. Further, in order to reduce the adhesion of dust to the magnetic recording layer coated on the light-sensitive material, the stabilizing solution described in JP-A-6-289559 can be preferably used. The amount of washing and replenishment of the stabilizing solution is preferably 80 to 1000 ml / m ² of the light-sensitive material, and particularly 100 to 5 ml.
00 ml, and more preferably 150 to 300 ml, are preferable ranges from the viewpoint of ensuring the washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment performed with such a supplement amount, thiabendazole, 1,2-benzisothiazolin-3one,
Known antifungal agents such as 5-chloro-2-methylisothiazolin-3-one and antibiotics such as gentamicin,
It is preferable to use water deionized with an ion exchange resin or the like. It is more effective to use deionized water in combination with antibacterial agents and antibiotics. Also, the liquid in the washing or stabilizing liquid tank is disclosed in JP-A-3-46652, JP-A-3-53246 and JP-A-3-53246.
It is also preferable to perform the reverse osmosis membrane treatment described in 55542, 3-121448, and 3-126030 to reduce the replenishment amount. In this case, the reverse osmosis membrane is preferably a low-pressure reverse osmosis membrane.

In the processing of the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in JIII Journal of Technical Disclosure, Japanese Patent No. 94-4992. In particular, a method of making a correction using the temperature and humidity information of the environment where the developing machine is installed is preferable based on (Equation-1) on page 2. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the replenishing water for washing.

As the treating agent used in the present invention, those described on page 3, right column, line 15 to page 4, left column, line 32 of the above-mentioned Kokai Giho are preferable. In addition, as a developing machine used for this,
The film processor described on page 3, right column, lines 22 to 28 is preferred. Specific examples of preferred processing agents, automatic processors, and evaporation correction methods for carrying out the present invention are described on page 5, right column, line 11 to page 7, right column, last line. .

The supply form of the treating agent used in the present invention is as follows:
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 have tablets and special tables
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid which has been prepared in advance in a concentration at the state of use. Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material in a container for containing these treatment agents. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers having a thickness of 500 to 1500 μm, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

Specific examples of the development processing for the color negative film used in the present invention include Fuji Photo Film Co., Ltd.
CN-16L, CN-16X, CN-16Q, CN manufactured by
-16FA processing solution and its replenishing solution, processing agent or Eastman Kodak C-41, C-41B, C
Examples of the treatment liquid include -41RA, its replenisher, and a treatment agent.

Next, the processing liquid for the color reversal film used in the present invention will be described. Regarding the processing for the color reversal film, known technology No. 6 (April 1, 1991), page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, 2 of Aztec Co., Ltd. It is described in detail in the line, and any of its contents can be preferably applied. In color reversal film processing, image stabilizers are included in either the conditioning bath or the final bath. Examples of such an image stabilizer include formalin, formaldehyde sodium bisulfite, and N-methylolazoles.
From the viewpoint of the working environment, sodium formaldehyde bisulfite or N-methylolazoles are preferable, and as N-methylolazoles, N-methyloltriazole is particularly preferable. The contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water, etc. described in the processing of the color negative film can be preferably applied to the processing of the color reversal film. A preferred color reversal film treating agent containing the above is E-manufactured by Eastman Kodak Company.
6 processing agents and CR-56 processing agents of Fuji Photo Film Co., Ltd. can be mentioned.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite ,, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic Alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co deposited γFe ₂ O
Co-coated ferromagnetic iron oxides such as ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably 20 m ² / g or more S _BET is the specific surface area, 30 m ²
/ g or more is particularly preferred. The saturation magnetization (σs) of a ferromagnet is
It is preferably from 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, and particularly preferably from 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 161032. Further, magnetic particles having a surface coated with an inorganic or organic material described in JP-A-4-259911 and 5-81652 can also be used.

The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer described in JP-A-4-219569, a natural product Coalescence (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3mol of isocyanate and 1m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable, and a combination thereof is also preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably from 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.
The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll,
Transfer rolls, gravure, kisses, casts, sprays, dips, bars, extrusions and the like can be used, and the coating solutions described in JP-A-5-341436 are preferred.

The magnetic recording layer has improved lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support preferably used will be described. For details, including the light-sensitive material, processing, cartridge and examples described later, open technical report, Japanese Patent No. 94-6023 (Invention Society; 1994.3.15). .)It is described in.
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to
It is 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web.
Surface irregularities may be imparted (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments are performed after forming the support, after surface treatment,
It may be carried out at any stage after application of the back layer (antistatic agent, slip agent, etc.) and after application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

In the present invention, the support is preferably surface-treated in order to bond the support and the light-sensitive material constituting layer. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4
-Dichloro-6-hydroxy-S-triazine, etc.),
Epichlorohydrin resin, active vinyl sulfone compound and the like can be mentioned. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10
μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
_{nO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
MoO ₃ , at least one selected from V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Fine particles of oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), and sol-like metal oxides or fine particles of these composite oxides. The content in the photosensitive material should be between 5 and
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to simultaneously add fine particles of 0.8 μm or less in order to enhance the matting property. Particles (0.25μm), colloidal silica (0.03μm)
Is mentioned.

Next, the film cartridge used for the light-sensitive material of the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and JP-A 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same size as the current 135 size, or the size of the current 135 size 25 mm cartridge can be reduced to 22 mm for miniaturization of the camera.
The following is also effective. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, the sensitive material of the present invention may be a patrone that rotates the spool to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. Also, the raw film and the developed photographic film may be stored in the same new cartridge or different cartridges.

[0091]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. Example 1 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co.) as an ultraviolet absorber, 300 ° C.
After melting at T, die is extruded from T-die and longitudinally stretched 3.3 times at 140 ° C, then transversely stretched 3.3 times at 130 ° C, and heat set at 250 ° C for 6 seconds to make PEN with a thickness of 92μm.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Yellow density 0.01, magenta density 0.08, cyan density
It was added to be 0.09. Furthermore, the support was wound around a stainless steel core having a diameter of 20 cm and subjected to a heat history of 113 ° C. for 30 hours to obtain a support with less winding tendency.

2) Coating of undercoat layer The above support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides thereof, and then gelatin (0.1 g / m ² ) and sodium α on each side. -Sulfodi-2-ethylhexyl succinate (0.01 g / m ² ), salicylic acid (0.025 g / m ² ).
m ² ), PQ-1 (0.005 g / m ² ), PQ-2 (0.006 g / m ² ), and apply an undercoat liquid (10 ml / m ² , using a bar coater) to stretch the undercoat layer. It was provided on the high temperature side. Drying is 115
It was carried out at 6 ° C for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A dispersion of fine particles of tin oxide-antimony oxide having an average particle size of 0.005 μm and a specific resistance of 5 Ω · cm (secondary agglomerated particle size: about 0.08 μm; 0.027). g / m ² ), gelatin (0.03 g / m ² ),
(CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ (0.02g / m ² ), poly (degree of polymerization
10) Oxyethylene-p-nonylphenol (0.005g /
m ² ), PQ-3 (0.008 g / m ² ), and resorcin. 3-2) Coating of magnetic recording layer 3-Poly (degree of polymerization 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g, Long axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² was diacetyl cellulose 1.15 g / m ² (iron oxide was dispersed by an open kneader and a sand mill), PQ-4 (0.075 g / m ² ), PQ-5 as a curing agent
(0.004 g / m ² ) was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone and dibutyl phthalate as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. _{C 6 H 13 CH (OH)} C 10 H 20 COOC 40 H 81 as sliding agent (50 mg / m
² ) and 5 mg / m ² and 15 mg / m ² of silica particles (average particle size 1.0 μm) as a matting agent and aluminum oxide (ERC-DBM manufactured by Reynolds Metal Co .; average particle size 0.44 μm) as abrasives Was added. Drying was carried out at 115 ° C for 6 minutes.
15 ° C). X- write saturation magnetization moment of the magnetic recording layer of the D color density increment of about 0.1 of ^B, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m, the squareness ratio in (blue filter) Was 65%.

3-3) Preparation of sliding layer Hydroxyethyl cellulose (25 mg / m ² ), PQ-6 (7.5
mg / m ² ), PQ-7 (1.5 mg / m ² ), and polydimethylsiloxane (B-3) 1.5 mg / m ² were applied. In addition, this mixture is
Xylene / propylene glycol monomethyl ether
It was melted in (1/1) at 105 ℃, poured into and dispersed in propylene monomethyl ether (10 times amount) at room temperature, and then made into a dispersion (average particle size 0.01μm) in acetone and then added. . Drying was carried out at 115 ° C. for 6 minutes (all the rollers in the drying zone and the conveying device were 115 ° C.). The sliding layer has a dynamic friction coefficient
0.10 (5 mmφ stainless hard ball, load 100 g, speed 6 cm /
Min), the coefficient of static friction was 0.09 (clip method), and the coefficient of dynamic friction between the emulsion surface and the sliding layer described later was 0.18, which were excellent characteristics.

[0095]

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4) Coating of Photosensitive Layer Next, a layer having the following composition was coated on the side opposite to the back layer obtained above to prepare a sample. This is designated as Sample 101. (Photosensitive layer composition) First layer (antihalation layer) Black colloidal silver Silver 0.15 Gelatin 2.00

Second Layer (Red Sensitive Emulsion Layer) Silver iodobromide emulsion (octahedral grain, core high iodine double structure, 1.62 average AgI content 6.0, average particle diameter equivalent to sphere 0.50 μm, diameter / Thickness ratio 1) Sensitizing dye A 6.8 × 10 ⁻⁴ Sensitizing dye B 3.2 × 10 ⁻⁵ Sensitizing dye C 9.6 × 10 ⁻⁴ Cyan coupler 0.92 Dibutyl phthalate 0.46 Gelatin 4 .00

Third Layer (Protective Layer) Hardener 0.16 Gelatin 4.00

The numbers corresponding to the above respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount per mol of silver halide in the same layer is shown in mol unit.

[0100]

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Sample 102 was prepared by adding Comparative Compound A to the first layer in a molar amount of 25 times the total number of moles of the sensitizing dye used in the second layer. Sample 10
3 was prepared by replacing comparative compound A with comparative compound B in an equimolar amount. Sample 104 is Comparative Compound A of Sample 102
Is a compound SR-13 represented by the general formula [SR] of the present invention.
Was also replaced by an equimolar amount.

Sample 105 was prepared by adding Comparative Compound C to the first layer of Sample 101 at a coating amount of 59.4 mg / m ² . Sample 106 was prepared by replacing Comparative Compound C of Sample 105 with Comparative Compound D in an equimolar amount. Samples 107 and 108 were prepared by replacing the comparative compound C of Sample 105 with the compounds represented by the general formulas (AI) and (AV) of the present invention, A-7 or A-65 in equimolar amounts, respectively. It was made. Comparative compounds A to D are shown in Chemical formula 18.

[0103]

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Hereinafter, as shown in Table 7, the comparative compounds A to D or the general formula [SR] and the general formula (A-
Samples 109 to 130 were prepared by substituting the compounds represented by I) to (AV) in equimolar amounts. The compounds represented by the general formulas (A-I) and (A-V) used in the second layer in Samples 116 to 120 and Samples 126 to 130 were added to couplers to prepare dispersions. The amount used is 1/3 of the coating amount of the first layer. The amount of the compound represented by the general formula [SR] added to the second layer was 5 times the molar amount of the whole sensitizing dye.

[0105]

[Table 7]

The prepared samples 101 to 130 are at 30 ° C.
After storing at 60% relative humidity for 7 days, cut and process,
It was used for the following tests. (1) Wedge exposure of white light remaining after color development processing was applied and the following color development processing was carried out. The developed sample was densitometrically measured for cyan (R) and magenta (G) densities. After measuring the concentration,
Immediately, it was washed with 38 ° C. washing water (flow rate of 500 ml / min) for 30 minutes, and the concentrations of R and G were measured again. For the same sample, the density difference between the sample immediately after color development and the sample further washed with water is the minimum density part (Dmin), Dmin +
When the difference in the exposure amount point of the sample immediately after color development giving a density of 0.5, Dmin +1.0 and Dmin +2.0 from the same exposure amount point of the sample further washed with water was examined, In the above concentration range, there was a substantially constant concentration difference. This constant density difference was defined as the residual color after color development. The larger the numerical value (the larger the density difference), the larger the residual color. Although the washing with water was further extended, it was separately confirmed that the concentration did not change even after 30 minutes. Table 7 shows the density difference (residual color) in the Dmin portion measured by the R and G densities. The color development process used in the above test is shown below.

First, Fuji Color Negative Super G40
0 (manufactured by Fuji Photo Film Co., Ltd.) was photographed with a camera, and the following treatment was performed for 15 days at a rate of 1 m ² per day (running treatment), and then the sample to be evaluated was treated. In addition, each processing is an automatic processor F manufactured by Fuji Photo Film Co., Ltd.
The following was carried out using P-360B. This FP-
The 360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992. The treatment process and the treatment liquid composition are shown below.

(Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C. 20 ml 17 liters Bleaching 50 seconds 38.0 ° C. 5 ml 5 liters Fixed (1) 50 seconds 38.0 ° C-5 liters Fixed (2) 50 seconds 38.0 ° C 8 ml 5 liters Water wash 30 seconds 25.0 ° C 17 ml 3.5 liters Stability (1) 20 seconds 25.0 ° C-3 liters Stabilization (2) 20 seconds 25.0 ° C 15 milliliters 3 liters Dry 1 minute 30 seconds 60 ° C * Replenishment amount per 35 m width of photosensitive material 1.1 m (24 Ex. 1 equivalent) Stabilizer (2) to (1) The countercurrent method was to flow into the fixing solution (2). The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 2.5 ml and 2.0 ml, respectively, per 1.1 mm width of 35 mm photosensitive material. , 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 c for color developer.
m ² , 120cm ^{2 for} bleaching solution, about 100c for other processing solutions
It was m ^2.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.3 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 2.0 2.0 Hydroxylamine sulfate 2. 4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.4 Add water to 1.0 liter 1.0 liter pH (hydroxylation Prepared with potassium and sulfuric acid) 10.05 10.18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ammonium Ferric Acid Monohydrate 118 180 Ammonium Bromide 80 115 Ammonium Nitrate 14 21 Succinic Acid 40 60 Maleic Acid 33 50 Water was added to 1.0 liter 1.0 liter pH [prepared with aqueous ammonia] 4.4 4.0

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium methanesulfinate 10 30 Ammonium methanethiosulfonate 4 12 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 7 20 Ethylenediaminetetraacetic acid 15 45 1.0 liter by adding water 1.0 liter pH [prepared with aqueous ammonia and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
Per liter or less, followed by 20 mg / liter of sodium diisocyanurate and 150 mg of sodium sulfate.
mg / l was added. The pH of this solution is 6.5 to 7.
5 range.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid diester Sodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 Add water to 1.0 liter pH 8.5

From Table 7, in Samples 101 to 104, the use of the compound SR-13 represented by the general formula [SR] of the present invention surely reduces the residual color measured in the R and G concentrations. But not enough. Also in Samples 105 to 108, by using the compounds represented by the general formulas (A-I) and (A-V) of the present invention, A-66 and A-3, the residual color measured at the R and G concentrations was obtained. It can be seen that the number is decreasing, but it is still not sufficient. These comparative samples 101
To 110, the samples 111 to 13 satisfying the constitution of the present invention.
At 0, the residual color measured by the R and G concentrations has a very small value or no value at all, and the residual color and the compound represented by the general formula [SR] to the general formula (AI) to
The combined use of the compounds represented by (A-V) shows a surprising effect of reducing the residual color.
It is clear from the comparison with 107 and 108.

Example 2 Using the support used in the preparation of the sample of Example 1, each layer of the following composition was multilayer-coated on the undercoat layer on the opposite side of the back layer by one-time simultaneous coating of all layers, A color negative film was prepared. This is designated as Sample 201.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 201) First layer (first antihalation layer) Black colloidal silver 0.08 Gelatin 0.70 Second layer (second antihalation layer) Black colloidal silver 0.09 Gelatin 1.00 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02

Third layer (intermediate layer) ExC-2 0.05 Polyethyl acrylate latex 0.20 Gelatin 0.70

Fourth Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.20 Silver iodobromide Emulsion B Silver 0.23 Silver iodobromide Emulsion C Silver 0.10 ExS-1 3.8 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.2 × 10 ^-4 ExC-1 0.17 ExC-2 0.02 ExC-3 0.030 ExC-4 0.050 ExC-5 0.020 ExC-6 0.010 ExC-10 0.045 Cpd-2 0.025 HBS-1 0.10 Gelatin 1.10

Fifth layer (medium-sensitive red-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.15 Silver iodobromide emulsion D Silver 0.46 ExS-1 4.0 × 10 ^-4 ExS-2 2.1 × 10 ^-5 ExS-3 5.7 × 10 ^-4 ExC-1 0.14 ExC-2 0.02 ExC-3 0.03 ExC-4 0.090 ExC-5 0.02 ExC-6 0.01 Cpd-2 0.05 HBS-1 0.10 Gelatin 0.75

Sixth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion 1.30 ExS-1 2.5 × 10 ^-4 ExS-2 1.1 × 10 ^-5 ExS-3 3.6 × 10 ^-4 ExC-1 0.12 ExC-3 0.11 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.40

Seventh layer (intermediate layer) Cpd-1 0.060 Solid disperse dye ExF-4 0.030 HBS-1 0.040 Polyethyl acrylate latex 0.15 Gelatin 1.10

Eighth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion F Silver 0.22 Silver iodobromide emulsion G Silver 0.35 ExS-7 1.4 × 10 ^-4 ExS-8 6.2 × 10 ^-4 ExS-4 2.7 × 10 ^-5 ExS-5 7.0 × 10 ^-5 ExS-6 2.7 × 10 ^-4 ExC-9 0.020 ExM-3 0.410 ExM-4 0.060 ExM-8 0.025 ExY-1 0.050 ExY-6 0.0070 HBS-1 0.30 HBS- 3 0.015 Gelatin 0.95

Ninth layer (medium-sensitive green-sensitive emulsion layer) Silver iodobromide emulsion G Silver 0.48 Silver iodobromide emulsion H Silver 0.48 ExS-4 4.8 × 10 ^-5 ExS-7 2.1 × 10 ^-4 ExS-8 9.3 × 10 ^-4 ExC-8 0.0020 ExC-9 0.0020 ExM-3 0.115 ExM-4 0.020 ExM-8 0.014 ExY-1 0.0090 ExY-4 0.0090 ExY-6 0.0050 HBS-1 0.13 HBS-3 4.4 × 10 ^-3 Gelatin 0.80

10th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.30 ExS-4 4.5 × 10 ^-5 ExS-7 1.2 × 10 ^-4 ExS-8 5.3 × 10 ^-4 ExC-1 0.021 ExM-1 0.010 ExM-2 0.020 ExM-5 0.0070 ExM-6 0.0050 ExM-7 0.012 Cpd-3 0.017 HBS-1 0.25 HBS-5 0.015 Polyethyl acrylate latex 0.15 Gelatin 1.33

Eleventh layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 ES-2 0.10 HBS-1 0.60 Gelatin 0.60

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.10 Silver iodobromide emulsion L Silver 0.25 ExS-9 8.4 × 10 ^-4 ExC-1 0.03 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.50 ExY-3 0.40 ExY-4 0.040 ExY-5 0.25 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 2.10

13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion M Silver 0.58 ExS-9 3.5 × 10 ^-4 ExY-2 0.050 ExY-3 0.070 ExY-4 0.0050 ExY-5 0.020 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.075 Gelatin 0.55

Fourteenth layer (first protective layer) Silver iodobromide emulsion N silver 0.10 UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-8 0.001 ExF-9 0.002 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 x 10 ^-2 Gelatin 1.8

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 0.04 B-2 (diameter 1.7 μm) 0.09 B-3 0.13 ES-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-4, B-4 to B- may be used. 6, F
-1 to F-9, F-12 to F-17, and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, and rhodium salt.

[0132]

[Table 8]

In Table 8, (1) Emulsions J to M were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions CE, GI, and M were subjected to gold sensitization and sulfur sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. And selenium sensitization. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) When a high-pressure electron microscope is used for the tabular grains, dislocation lines as described in JP-A-3-237450 are observed. (5) Emulsions A to E, G, H and J to M are Rh, Ir, F
e in an optimal amount. The tabularity is defined as Dc / t ² , where Dc is the average equivalent circle diameter in the projected area of the tabular grains and t is the average thickness of the tabular grains.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

[0136]

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[0137]

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[0138]

[Chemical 21]

[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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Next, Sample 202 is a compound S represented by the general formula [SR] of the present invention in the intermediate layer of the third layer of Sample 201.
The total molar amount of the spectral sensitizing dyes (ExS-1 to ExS-3) in which R-9 was used in the fourth to sixth all-red sensitive emulsion layers was 20.
Spectral sensitizing dye (ExS) containing double molar amount of the same compound in the 7th layer intermediate layer was used in the 8th to 10th all-green emulsion layers.
-4 to ExS-8) was added in an amount 20 times the total molar amount. Sample 203 is the third layer and the seventh layer of Sample 101.
The compound A-57 represented by the general formula (AI) of the present invention was added to both intermediate layers of the layer so that the coating amount was 67.5 mg / m ² . Sample 204 is the same as sample 203 in the intermediate layers of the third layer and the seventh layer of sample 202, but with A-57 of 67.
It was prepared by adding so that the coating amount was 5 mg / m ² . Sample 2
No. 05, the compound A-2 represented by the general formula (A-V) was added to each of the fourth to sixth red sensitive emulsion layers of the sample 204.
A coating amount of 6 mg / m ² was prepared by adding the same compound to the eighth to tenth green sensitive emulsion layers so that the coating amount was the same. Sample 206 was prepared by replacing A-2 used in sample 205 with A-55 in an equimolar amount. A-55 was used as an emulsified dispersion in addition to the coupler. Hereinafter, as shown in Table 9, the compounds represented by the general formula [SR] and the compounds represented by the general formulas (A-I) to (A-V) were added to the third layer to the tenth layer up to Sample 210. Was produced. General formula [S
R] red-sensitive emulsion layer of the compound represented by R] (4th to 6th layers)
And the amount used for the green-sensitive emulsion layer (8th to 10th layers),
The spectral sensitizing dye used in each layer was added in an amount of 3 times the coating amount with respect to the total molar amount. Compounds A-4, A-39, A-49: A-50, A-55 and A-60 were each used as an emulsified dispersion in addition to the coupler, similar to the above-mentioned A-55. A-62
Was used as an emulsified dispersion by increasing the amount of HBS-1 used in the same layer as these compounds to a weight ratio of 1.0 and mixing them with other oil-soluble compounds.

[0155]

[Table 9]

The produced samples 201 to 210 were cut and processed, and then the following tests were carried out on the residual colors in accordance with the method for examining the residual colors after the color development processing of Example 1. The sample was exposed to a wedge of white light and subjected to the following color development processing, and immediately, the densities of cyan (R), magenta (G) and yellow (B) were measured, and then 4 again.
Rinsing with 0 ° C. washing water (flow rate of 500 ml / min) for 30 minutes was performed, and the R, G, and B concentrations were measured. From these samples,
For the same sample, the difference in density at each point of the same exposure amount between the sample immediately after color development and the sample washed with additional water was determined.
The density differences of R, G, and B were almost constant from the minimum density area to the maximum reached density area of the color image area in the same manner as in Example 1. This constant density difference is shown in Table 9 above as the residual color. The larger the numerical value (the larger the density difference), the larger the residual color. The residual color was examined by further extending the washing with water, but no change in the density difference was observed even after 30 minutes. The color development processing used in this embodiment is shown below. First, as in Example 1, a Fuji Color Negative Super G400 photographed with a camera was taken 1 day a day.
The sample of this example was treated after m ² for 15 days.

(Treatment Step) Step Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ° C. 20 ml 10 liters Bleach 45 seconds 38.0 ° C. 5 ml 5 liters Settling (1) 45 seconds 38 0.0 ℃ -5 liters Fixed (2) 45 seconds 38.0 ℃ 30 ml 5 liters Stabilized (1) 20 seconds 25.0 ℃ -5 liters Stabilized (2) 20 seconds 25.0 ℃ -5 liters Fixed (3) 20 seconds 25.0 ° C 20 ml 5 liters Dry 1 minute 55 ° C * Replenishment amount per 35 mm width 1.1 m (24 Ex. 1 equivalent) * Fixing from (2) to (1) Flow method * Stable is the countercurrent method from (3) to (1). The amount of developer brought into the bleaching process and the amount of fixer brought into the stabilizing process are per 1m length of 35 mm wide photosensitive material. 2.5 ml, It was 2.0 milliliters.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.5 0.5 Iodine Potassium iodide 1.2 mg-hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.7 6.2 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.00 10.15

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ammonium Ferric Acid Monohydrate 144.0 206.0 1,3-Diaminopropanetetraacetic Acid 2.8 4 0.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Ammonia water (27%) 10.0 1.8 Acetic acid (98%) 51.1 73.0 Potassium carbonate 10.0-Add water 1.0 liter 1.0 liter pH (adjusted with aqueous ammonia and acetic acid) 4.3 3.4

(Fixing Solution) Common to Tank Solution and Replenishing Solution (unit: g) Ethylenediaminetetraacetic acid disodium salt 1.7 Sodium sulfite 14.0 Sodium bisulfite 10.0 Ammonium thiosulfate aqueous solution (700 g / liter) 210.0 ml Thiocyan Ammonium acid 163.0 Thiourea 1.8 Water was added to 1.0 liter pH 6.5

(Stabilizer) Common to tank liquid and replenisher (unit: g) Surfactant 0.2 [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] Polymaleic acid (average molecular weight 2000) 0 0.1 1,2-benzisothiazolin-3-one 0.05 hexamethylenetetramine 5.5 Water was added to 1.0 liter pH 8.5

From the results shown in the table, it is clear that the samples 204 to 210 satisfying the constitutional requirements of the present invention have less residual color or no residual color as compared with the comparative samples 201 to 203. Especially,
Comparative sample of samples 202 and 203 and inventive sample 20
4, the effect of reducing the residual color is increased by the combined use of the specific stilbene compound of the present invention and the specific hydroxylamine derivative. Further, even in the sample of the present invention, these It can be seen that it is preferred to use the compounds in both the light-sensitive and light-insensitive layers. Separately, it is processed into the current 135 size, the same subject is photographed by the camera under the same exposure conditions, and these are color-developed. These are used as color negative films in Fuji Color Paper and Super FAV (Fuji Photo Film Co., Ltd. products). Print, CP-45X
Color paper processing liquid (also Fuji Photo Film Co., Ltd.)
When the product was developed and processed and the pattern was compared and observed,
In the comparative sample, particularly in the sample 201, it was observed that the entire pattern including the white background was magenta.

Example 3 The support used in Example 2 was replaced with an undercoated cellulose acetate support (film thickness 127 μm), and Samples 301 to 301 having the same layer constitution and composition as Samples 201 to 210 were prepared. When 310 is produced and the same performance evaluation as in Example 2 is performed, the same tendency as the result obtained in Example 2 can be obtained, and the sample can be a color-developed sample with less residual color. .

[0164]

The stilbene compound having a specific triazine ring represented by the general formula [SR] and the general formulas (A-I) to (A) are used in the photosensitive layer and the non-photosensitive layer of the color light-sensitive material.
By using the specific hydroxylamine derivative represented by -V), the residual color after the color development processing is reduced,
A silver halide color photographic light-sensitive material capable of improving the color reproducibility of a color positive image can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03C 7/00 520 G03C 7/00 520 530 530 (72) Inventor Masato Taniguchi 210 Nakanuma, Minamiashigara, Kanagawa Prefecture Address Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing a compound represented by the general formula (SR), and A silver halide color photographic light-sensitive material containing a compound selected from the group of compounds represented by (A-I) to (A-V). Embedded image In the general formula [SR], L ¹ and L ² may be the same or different and are represented by —OR ¹ or —NR ² R ³ (R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group), And, at least one of the following conditions is satisfied. Four substituents L ¹ and L in the general formula [SR]
² has a total of four or more substituents selected from the general formula [A] group. Four substituents L ¹ and L in the general formula [SR]
² has a total of two substituents selected from the general formula [A] group, and has a total of two or more substituents selected from the general formula [B] group. Embedded image In the general formula [A] group, X represents a halogen atom and R represents an alkyl group. In the general formulas [SR] and [A],
M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium. In the general formula [B] group,
R, R ′ and R ″ are hydrogen atoms or alkyl groups,
R'and R "may be linked to each other to form a ring. In formula (AI), R _a1 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, It represents an alkoxycarbonyl group or an aryloxycarbonyl group, and R _a2 represents a hydrogen atom or the group represented by R _a1 . Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. . _Ra1 and _Ra2 may combine with each other to form a 5- to 7-membered ring. In formula (A-II), X represents a heterocyclic group, R _b1 is an alkyl group,
Represents an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring. In the general formula (A-III), Y represents a nonmetallic atom group necessary for forming a 5-membered ring together with -N = C-. Y represents a group of non-metal atoms necessary for forming a 6-membered ring together with a -N = C- group, and the terminal of Y bonded to the carbon atom of the -N = C- group is -N (R _c1 ). -, -C (R _c2 ) (R _c3 )-, -C (R _c4 ) =,
A group selected from -O- and -S- (on the left side of each group,
(Bonded to a carbon atom of N = C-). R _c1 ~ R _c4
Represents a hydrogen atom or a substituent. In formula (A-IV), R _d1 and R _d2 may be the same or different and each represents an alkyl group or an aryl group. However,
R _d1 and R _d2 are simultaneously an unsubstituted alkyl group, and R
_{When d1} and R _d2 are the same group, R _d1 and R _d2 are alkyl groups having 8 or more carbon atoms. In the general formula (A-V), R
_e1 and R _e2 may be the same or different and each is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group or an aryl group. Represents Where _Re1 and _Re2
Are simultaneously -NHR _e3 (R _e3 is an alkyl group or an aryl group)
Never be. R _a1 and R _a2 , or X and R _b1 may be bonded to each other to form a 5- to 7-membered ring.