JPH09152689A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain good photographic characteristic including high sensitivity and gradation and less fogging, to prevent color mixing and to suppress color staining, such as color increasing by incorporating specific couplers into the photographic sensitive material and incorporating a specific non-color developable and diffusion resistant compd. therein. SOLUTION: This photographic sensitive material has respectively at least one layer of photosensitive silver halide emulsion layers and non-photosensitive layers on a base. The specific 2-equivalent couplers expressed by formula I and the specific hydrazine compds. expressed by formula II are incorporated therein. In the formula I, R1 denotes a ternary alkyl group; R2 denotes a halogen atom, alkoxy group, etc., R3 denotes an alkoxy carbonyl group, alkylsulfonyloxy group; R4 denotes a halogen atom, alkyl group, etc.; m denotes an integer from 0 or 2; R5 , R6 denote hydrogen atoms, alkyl group; X denotes an oxygen atom, sulfur atom, etc. In the formula II, X denotes -N(R1 )R3 (where R<1> is a hydrogen atom, etc., R<3> is a hydrogen atom, etc.); R<2> denotes a hydrogen atom, aliphat. group, etc.; R<5> denotes a hydrogen atom, alkyl group, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. Specifically, it provides high sensitivities and good photographic properties with less gradation and fogging, and prevents color contamination such as color mixing and post-coloring (bleaching fog) after color development, and improved color reproducibility. The present invention relates to a color photographic light-sensitive material.

[0002]

2. Description of the Related Art In silver halide color photographic light-sensitive materials, especially color photographic materials for photography, it is strongly demanded that they have high sensitivity and excellent image quality such as color reproducibility, and their research and development are being earnestly pursued. . Even in the yellow couplers used for the current color photographic material for photographing based on the subtractive color method, the above-mentioned demand is not yet satisfied, and further improvement is desired. In particular, the yellow coupler used in the color negative photosensitive material is a 2-equivalent benzoylacetanilide type coupler (hereinafter, abbreviated as BA type coupler).
Is the mainstream. This BA-type coupler has a higher coupling activity than the two-equivalent pivaloylacetanilide-type coupler (hereinafter referred to as PA-type coupler), which is another typical yellow coupler used, and the molecule of the dye to be produced. It has the excellent property of having a high extinction coefficient. However, on the other hand, the spectral absorption characteristics of the obtained dye are large in absorption in the green light region on the long wavelength side, which is disadvantageous in color reproduction. In addition, the fastness of the color image is higher than that of the PA type coupler. It has the disadvantage of being inferior. A coupler having excellent properties of both couplers has not yet appeared at present, and it is desired to develop a coupler that can satisfy these excellent properties even a little. The yellow coupler according to the present invention is a coupler which belongs in part to the above-mentioned PA type coupler, and is described, for example, in US Pat.
451 and 492. This type of coupler is characterized by a so-called ballast group, and is characterized by a leaving group portion substituted at the coupling active position.
The coupling activity is higher than that of the A-type coupler, and it is preferable in that it compensates for some of the disadvantages of the PA-type coupler. However, although the coupling activity became higher and it became advantageous for higher sensitivity, there was a problem that fog increased with it, and further color development after bleaching after color development in color development processing (bleach fog) In addition, when the light-sensitive material after color development processing was stored with time, there was a problem that the yellow minimum density portion of the uncolored portion increased, and it was found that its use would be difficult unless these problems are solved.
In the case of a multi-layer color negative photosensitive material, due to its high coupling activity, the color developing agent oxidized during color development diffuses from other layers having different color sensitivities, and the originally unexposed areas that do not develop color diffuse. It has also been clarified that the problem that undesired color formation due to the coupling reaction with the oxidized product of the developing agent, resulting in color mixture and remarkably impairing the color reproducibility is also a problem to be solved.

On the other hand, as one means for solving the above-mentioned problems, it is known to use a compound which is capable of scavenging an oxidized product of a color developing agent, which is called a color mixing inhibitor, and many compounds are known. Is proposed. These compounds are roughly classified into mono- or polyhydroxybenzene derivatives, for example, sulfonamidophenol-based derivatives (eg, US Pat. No. 4,205,987), hydroquinone and catechol derivatives (eg,
US Pat. Nos. 2,728,659 and 3,700,4
53, No. 4,198,239, etc.) and pyrogallol derivatives (for example, US Pat. No. 4,474,874 etc.), and hydroquinone derivatives are representative thereof. A compound represented by the other is a hydrazine derivative, for example, EP 338785,
There is JP-A-5-232651. Some of these representative compounds are used in the current color photographic light-sensitive materials, and some of the above problems can be solved to some extent, but fog reduction and color reproducibility are improved. However, it is not satisfactory, and there is a problem in that increasing the amount used adversely affects the photographic property such as sensitivity deterioration and the sharpness deterioration. In particular, the hydroquinone derivative has a problem in the stability of the compound, and when the compound is subjected to air oxidation or color development treatment, the oxidant of the compound becomes a colored substance, causing color contamination and impairing color reproducibility. However, there have been problems such as uneven coloring and adverse effects on the latent image when the photosensitive material is aged. Further, the above-mentioned problems such as bleaching fog and color increase after color development processing are not satisfactory, and are problems to be solved.

[0004]

SUMMARY OF THE INVENTION Therefore, the present invention provides high sensitivity and good photographic properties with less gradation and fog, and prevents color mixture, resulting in bleaching fog and color increase when the photographic material after development is aged. It is an object of the present invention to provide a silver halide color photographic light-sensitive material that suppresses color contamination such as the above and has improved color reproducibility.

[0005]

Means for Solving the Problems As a result of earnest studies, the inventors of the present invention have provided the above-described high-sensitivity, hard gradation, and photographic properties with little fog, and have not caused color mixture or bleaching fog and undeveloped color over time after processing. In order to suppress color contamination such as color increase of parts and improve color reproducibility, the constituent layers of a color light-sensitive material having at least one photosensitive silver halide emulsion layer and a non-photosensitive layer on a support, respectively. Using a 2-equivalent yellow coupler in which one of the hydrogen atoms at the active position of the acetanilide type coupler substituted with an acyl group having a specific tertiary alkyl group in at least one layer has a specific leaving group, and has a specific non-color-forming property. Found that it can be achieved by a silver halide color photographic light-sensitive material using a human-razine-based compound that is stable and diffusion resistant,
The present invention has been completed. That is, the present invention

The embodiment (1) is a color light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive layer on a support, and a specific photosensitive material represented by the general formula [I]. Contains 2 equivalents of a yellow coupler, and
It is a color photosensitive material containing a specific hydrazine compound represented by the general formula (H).

[0007]

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In the general formula [I], R ₁ is a tertiary alkyl group, R ₂ is a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an alkylsulfonyloxy group,
Or a cycloalkyl group, R ₃ is an alkoxycarbonyl group, or an alkylsulfonyloxy group, R ₄ is a halogen atom, an alkyl group, an alkoxy group, a carbonamido group, or a sulfonamide group, and m is an integer of 0 to 2. , R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group, and X represents an oxygen atom, a sulfur atom or an imino group.

[0009]

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In the general formula (H), X--N (R ¹ ) R
³ or represents -OR ^4, wherein R ¹ is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic residue, R ^3, R ⁴ represents a group removed a hydrogen atom or an alkali conditions . R
² is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a nitro group or a hydrazino group, and X and R ² may combine to form a ring. R ⁵ represents a hydrogen atom, an alkyl group or a group removed under alkaline conditions. R ¹ ,
^Two or more formulas (H) may be bonded at the R ² or R ⁵ moiety to form an oligomer or polymer. G is -CO
-, - COCO -, - SO 2 -, - SO -, - CON
^{(R 6) -, - COO} -, - COCON (R 7) -, -
^{COCOO -, - PO (R 8} ) -, - PO (OR 9)
Represents a —, —PO (OR ¹⁰ ) O—, — (C═S) — or iminomethylene group, wherein R ⁶ and R ⁷ are a hydrogen atom, an alkyl group or an aryl group, and R ⁸ , R ⁹ and R ¹⁰ is an alkyl group or an aryl group. By applying such a specific 2-equivalent yellow coupler and a specific hydrazine-based compound to a color light-sensitive material, it is possible to make use of the high coupling activity of the 2-equivalent yellow coupler and to provide high-sensitivity and high-contrast photographic properties. Fog can be reduced by using a specific hydrazine-based compound which is a so-called color mixing inhibitor, and after-color development (bleach fog) caused by the bleaching process of the color development process or when the sensitized material after the color development process is stored with time. Prevents color contamination such as increased yellow density in uncolored areas, and color mixing in multilayer color light-sensitive materials,
Excellent color reproducibility can be provided, and the object of the present invention can be achieved excellently.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION First, the yellow coupler of the present invention will be described in detail below. In the general formula [I], R ₁ is preferably a tertiary alkyl group having 4 to 16 carbon atoms, and even if it has a monocyclic or polycyclic structure, a substituent (for example, a halogen atom, an aryl group, It may have an alkoxy group or an aryloxy group). Specific examples of R ₁ include t-butyl group, 1-methylcyclopropane-
1-yl group, 1-ethylcyclopropan-1-yl group,
1-benzylcyclopropan-1-yl group, 1-methylcyclobutan-1-yl group, 1-methylcyclopentan-1-yl group, 1-methylcyclohexane-1-yl group, 2,2,5-trimethyl- 1,3-dioxane-5
-Yl group, bisiloku [2,1,0] pentan-1-yl group, bicyclo [2,2,0] hexan-1-yl group, bicyclo [3,1,0] hexan-1-yl group, bicyclo [4,1,0] heptan-1-yl group, bicyclo [1,
1,1] Pentan-1-yl group, bicyclo [2,1,
1] Hexane-1-yl group, bicyclo [2,2,1] heptan-1-yl group, bicyclo [2,2,2] octane-1-yl group, and adamantane-1-yl group.

In the general formula [I], R ₂ is preferably a halogen atom (F, Cl, Br, I) and has 1 to 1 carbon atoms.
24 alkoxy groups (eg, methoxy group, butoxy group,
Tetradecyloxy group), an aryloxy group having 6 to 24 carbon atoms (for example, phenoxy group, p-methoxyphenoxy group, p-t-octylphenoxy group), an alkyl group having 1 to 8 carbon atoms (for example, methyl group, Ethyl group, isopropyl group, t-butyl group, benzyl group, trifluoromethyl group), or cycloalkyl group having 3 to 8 carbon atoms (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group), 1 to 24 carbon atoms Is an alkylsulfonyloxy group (eg, methylsulfonyloxy group, hexadecylsulfonyloxy group).

In the general formula [I], R ₃ is preferably an ether oxygen atom having 6 to 30 carbon atoms or an optionally esterified alkoxycarbonyl group or alkylsulfonyloxy group. R ₃ may have a substituent (for example, a halogen atom, an aryl group, an aryloxy group). R ₃ is preferably a group having a size and shape sufficient to impart resistance to diffusion in a hydrophilic colloid to the yellow coupler represented by the general formula [I]. R ₃
The substitution position of is preferably the 3-position, 4-position, or 5-position on the benzene ring, and particularly preferably the 5-position.

In the general formula [I], R ₄ is preferably a halogen atom (F, Cl, Br, I), having 1 to 1 carbon atoms.
8 alkyl groups (eg methyl, isopropyl, t
-Butyl group), an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, butoxy group, benzyloxy group), a carbonamido group having 1 to 8 carbon atoms (eg, acetamido group, benzamido group), or the number of carbon atoms 1 to 8 sulfonamide groups (eg, methanesulfonamide group, p-toluenesulfonamide group).

In the general formula [I], m is an integer of 0-2. When m is an integer of 1 or 2, the substitution position of R ₄ is preferably the 3-, 4-, or 5-position on the benzene ring.

In the general formula [I], R ₅ and R ₆ are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, butyl group, hexyl group).
It is.

In the general formula [I], X is preferably an oxygen atom.

Particularly preferred embodiments of the coupler of the present invention are as follows. That is, in the general formula [I],
R ₁ is a t-butyl group, 1-alkylcyclopropane-1
-Yl group, or 5-alkyl-1,3-dioxane-
5-yl group, more preferably t-butyl group or 1-alkylcyclopropan-1-yl group, and particularly preferably t-butyl group. R ₂ is a halogen atom or an alkoxy group. R ₃ has 8 to 24 carbon atoms
Is a linear or branched alkyl group which may be separated by an ether oxygen atom or ester. R ₄
Is a halogen atom or an alkoxy group. m is an integer of 0 or 1. When m is 1, the substitution position of R ₄ is 3
Position or fourth position is preferred. R ₅ and R ₆ are a hydrogen atom or an alkyl group having 1 to 4 hydrogen atoms. General formula [I]
Of the couplers represented by, particularly preferred couplers are represented by the following general formula [II].

[0019]

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In the general formula [II], R ₁ , R ₂ , R
₃ , R ₄ , R ₅ , R ₆ and X are respectively the same as R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and X in the general formula [I], and n is 0 or Represents an integer of 1.

Specific examples of the yellow coupler of the present invention are shown below, but the present invention is not limited thereto.
In the following table, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , X, and m are according to general formula [I].

[0022]

[Chemical 6]

[0023]

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[0024]

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[0025]

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The yellow coupler of the present invention is disclosed in JP-A-55 / 55.
-598, 56-87041, JP-A-4-218.
042, 4-344640, 5-53269.
, No. 5-80469, Research Disclosure No. 18053 (1979), EP
It can be synthesized by the method described in No. 672,946A or the like.

The yellow coupler of the present invention can be added to any layer of a light-sensitive material, but in a multilayer color light-sensitive material, it is particularly preferably added to a blue-sensitive silver halide emulsion layer or its adjacent non-light-sensitive layer. . The amount of coupler added is 0.01 mmol to 10 mmol, preferably 0.1 mmol to 5 mmol, and more preferably 0.2 to 2 mmol per m ² of the light-sensitive material.

The yellow coupler of the present invention can be used together with other known yellow couplers such as benzoylacetanilide type coupler, malondianilide type coupler, dialkylcarbamoylacetanilide type coupler and 1-indolinylcarbonylacetanilide type coupler. it can. The yellow coupler of the present invention can be added to a light-sensitive material by, for example, a method of preparing a coupler dispersion by an oil-in-water dispersion method described in US Pat. No. 2,322,027 and adding the dispersion to a coating solution. Done. It is desirable that the weight ratio of the high boiling organic solvent to the coupler used in the oil-in-water dispersion method is small. Preferably it is 2.0 or less. 1.0 or less is more preferable, and especially preferable is 0.5 or less. The lower limit may be a dispersion in which no high boiling organic solvent is used. Further, a latex dispersion method can also be applied. It is preferable that the weight ratio of the high boiling point organic solvent to the coupler be small in order to reduce the residual amount of the developing agent remaining in the oil droplets after the color development processing. This is because the remaining developing agent undergoes air oxidation during storage and undergoes a coupling reaction with the coupler remaining in the undeveloped portion to form a yellow dye. In particular, the coupler of the present invention is strongly affected by the high activation. It is also preferable in that the thickness can be reduced and sharpness can be improved.

The yellow coupler of the present invention has higher coupling activity than the conventional acetanilide type 2-equivalent coupler substituted with an acyl group having a tertiary alkyl group. Accordingly, it exhibits high sensitivity and high contrast photographic properties and gives good color development.
This high coupling activity is provided by the introduction of a ballast group that imparts specific diffusion resistance to the anilide nucleus of the acetanilide mother nucleus substituted by the acyl group having the specific tertiary alkyl group, and the coupling active site This is because one of the hydrogen atoms is substituted with a specific leaving group.
The coupler of the present invention can increase the coupling activity as described above, and is currently a benzoylacetanilide type 2 which is a mainstream coupler for color negative photosensitive materials.
In contrast to an equivalent weight coupler, the molecular weight of the coupler can be reduced by introducing a mother nucleus and a specific low-molecular weight leaving group, thereby reducing the coating weight of the coupler per unit area coated on the light-sensitive material. It can be made thin. Next, the general formula (H) will be described in more detail. The aliphatic group of R ¹ and R ² has 1 to 1 carbon atoms.
30 is a linear, branched or cyclic alkyl group, an aralkyl group, an alkenyl group or an alkynyl group, and the alkyl group is a linear, branched or cyclic group having 1 to 30 carbon atoms, such as methyl. , Cyclohexyl, 2-octyl, octadecyl. The aralkyl group has a carbon number of 7 to 30, and examples thereof include benzyl, phenethyl and trityl. The alkenyl group has 2 to 30 carbon atoms and is, for example, vinyl or 1-dodecenyl. The alkynyl group has 2 to 30 carbon atoms and is, for example, ethynyl, octynyl or phenylethynyl. R ¹ , R ²
The aromatic group is an aryl group having 6 to 30 carbon atoms, such as phenyl and naphthyl. The heterocyclic group for R ¹ and R ² may be a saturated or unsaturated, monocyclic or condensed ring, and examples thereof include pyridyl, imidazolyl, thiazolyl, quinolyl, morpholino and thienyl.

As the hydrazino group of R ² , R of the formula (H) is used.
^{1 N (R 3) -N (} R 5) - and the like. R ³ , R ⁴ , R
A group that can be removed under alkaline conditions of ⁵ has 2 carbon atoms.
An alkylsulfonyl group, an arylsulfonyl group, an acyl group, a dialkylaminomethyl group, a hydroxymethyl group and the like, which are 0 or less, can be mentioned. The alkyl of R ^{5 is} the same as that described for R ¹ , and R ^{3 to} R ⁵ are preferably a hydrogen atom. R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
The alkyl group of ¹⁰ has a carbon number of 1 to 20, and examples thereof include methyl, cyclohexyl and dodecyl. R ⁶ , R
^7, the aryl group of ^{R 8, R 9, R 10} , phenyl, naphthyl at 6 to 20 carbon atoms. If possible, the groups described above may have a substituent, and as the substituent, an alkyl group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, a hydroxy group, a carboxyl group. , Aryl group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, acyl group, halogen atom, cyano group, heterocyclic group or sulfo group.

Particularly when R ¹ is an aromatic group, the substituent is preferably an electron-donating group, and examples thereof include an acylamino group, a sulfonylamino group, a ureido group, a urethane group or an alkoxy group. The diffusion resistance of the general formula (H) means that it contains a ballast group or a group that enhances adsorption to silver halide. Examples of the ballast group include ballast groups commonly used in immobile photographic materials such as couplers. In that case, it is more preferable to have a polar group as a substituent. As a polar group,
A group having a π value smaller than −1.0 in combination is, for example, hydroxy, sulfonamide, amino, carboxy, carbamoyl, sulfamoyl, ureido or heterocyclic group. When it contains a ballast group, the molecular weight of the general formula (H) is 30.
It is 0 to 1500, preferably 450 to 1500, and more preferably 500 to 800. Examples of the group that enhances the adsorption on the silver halide surface include a thiourea group, a mercaptoheterocyclic group and an azole group. As the diffusion resistant group, it is more preferable to have a ballast group rather than a silver halide adsorption group.

As G in the general formula (H), --CO-- and-
_{COCO -, - SO 2 -,} - SO -, - CON (R 6)
-, - COO -, - PO (R 8) -, - PO (OR 9)
-, or -PO (OR ¹⁰⁾ O- are preferable, -CO
-, - COCO -, - CON (R 6) -, - PO
(R ⁸ )-, -PO (OR ⁹ )-, -PO (OR ¹⁰ ) O
-Or -COO- is more preferable, -CO-, -P
O (OR ¹⁰⁾ O- is most preferable. Among the compounds represented by the general formula (H), the compounds represented by the following formulas (HI) to (HV) are preferable.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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In the formula, R ¹¹ and R ²¹ have the same meanings as R ^{1 in} formula (H), G ¹¹ , G ³¹ , G ⁴¹ and G ⁵¹ have the same meanings as G, R ¹³ , R ²³ ,
R ³³ has the same meaning as R ³ , R ⁴⁴ has the same meaning as R ⁴ , R ¹⁵ , R ²⁵ and R
³⁵ , R ⁴⁵ and R ⁵⁵ are synonymous with R ⁵ , m ¹ , m ⁴ and m ⁵ are m
And X ⁵¹ is synonymous with X. R ¹² is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or a hydrazino group,
²² is a cyano group, a nitro group, a perfluoroalkyl group (having 1 to 30 carbon atoms, for example, trifluoromethyl, perfluorooctyl) or a heterocyclic group, and R ⁴² is an aliphatic group, an aromatic group, a hetero group. It is a cyclic group. Z ^{31 in the} formula (H-III) is methylene, ethylene, trimethylene,
CO-, 1,2-phenylene, -O-, -S-, -NH
Examples of the divalent linking group include-, -NHNH- and combinations thereof, and the ring is preferably a 5- to 8-membered ring. Equation (H
In —V), R ⁵¹ is a hydrogen atom, a halogen atom or an alkyl group, and L ⁵¹ is —CO—, —SO ₂ —, —NH.
-, -O-, -S-, phenylene, alkylene and a divalent linking group consisting of a combination thereof, L ⁵² is a divalent group obtained by removing a hydrogen atom from R ¹ of the formula (H),
r and t are 0 or 1. Among the formulas (HI) to (HV), the following formula (H-VI) is more preferable.

[0039]

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In the formula, R ⁶¹ is an aromatic group, R ⁶² is an aliphatic group, an aromatic group or a heterocyclic group, and G ⁶¹ is --CO-- or --C.
^{OCO -, - CON (R 66} ) -, - COO -, - PO
(R ⁶⁸ )-, -PO (OR ⁶⁹ )-, or -PO (OR
⁶¹⁰ ) O-. Here, R ⁶⁶ has the same meaning as R ^{6 in} formula (H), R ⁶⁸ has the same meaning as R ^{8 in} formula (H),
R ⁶⁹ has the same meaning as R ^{9 in} formula (H), and R ⁶¹⁰ has the same meaning as R ^{10 in} formula (H). R ⁶¹ , R ⁶² , R ⁶⁹ or R ⁶¹⁰ contains a ballast group. Furthermore, the formula (H-VII) or (H-VIII) shown below is most preferable.

[0041]

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In the formula, R ⁷¹ and R ⁷³ are substituents on the benzene ring, and examples thereof include those mentioned as the substituents for R ^{1 in} the general formula (H), particularly those having an electron donating property (acylamino, ureido). , Sulfonylamino, alkoxy are preferred, R ⁷² and R ⁷⁴ are aliphatic or aromatic groups.
Either R ⁷¹ or R ⁷² , R ⁷³ or R ⁷⁴ has 8 carbon atoms
It has the above ballast groups. Preferably R ⁷¹ or R ⁷² ,
R ⁷³ or R ⁷⁴ has a polar group. Two R ^{74 s} in formula (H-VIII) may be the same or different, and may be linked to each other to form a ring.

The synthesis of the compound represented by the general formula (H) of the present invention can be carried out, for example, in JP-A-3-164,735 and 3-15.
4,051, the same 3-150,560, the same 3-150,5
62, 1-315, 731, or the method of the patent cited.

Specific examples of the compound represented by formula (H) of the present invention are shown below, but the invention is not limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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The compound represented by the general formula (H) (color mixing inhibitor) of the present invention can be used in any of the layers constituting the light-sensitive material. When the color mixing inhibitor of the present invention is used for the purpose of preventing color fog such as fog, bleach stain, and yellow density increase in the uncolored part over time after color development processing, a layer containing the yellow coupler of the present invention or It is preferably added to a non-photosensitive layer (intermediate layer, yellow filter layer, protective layer, etc.) adjacent to the layer containing the coupler. When used for the purpose of preventing color mixing, it is preferably added to a non-photosensitive layer (intermediate layer) provided between silver halide emulsion layers having different color sensitivities. Further, when it is used for both the purpose of preventing color fogging and preventing color mixing, it can be added to two or more layers of both the yellow coupler-containing layer and the non-photosensitive layer of the present invention. Also, a plurality of color mixing inhibitors can be mixed and used.

The amount of the color mixing inhibitor of the present invention added is 1 × 10 ⁻³ to 1 × 10 ⁻⁶ mol / m ² per layer.
When this color mixing inhibitor is used for the purpose of preventing color fog, the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻⁶ mol / m ² per layer is preferable, and when it is used for the purpose of preventing color mixing, 1 x 10
^{The range of −3} to 1 × 10 ⁻⁵ mol / m ² is preferable. Further, the color mixing inhibitor of the present invention can be used in combination with known color mixing inhibitors other than the present invention depending on the performance required for the light-sensitive material. These can be used as a mixture. It can be used individually in separate layers. Known color mixing inhibitors other than the present invention include, for example, the above-mentioned hydroquinone derivatives, gallic acid derivatives, aminophenol derivatives, other ascorbic acid derivatives, and sulfonamide derivatives.

In order to introduce the color mixture inhibitor of the present invention into the constituent layers of the light-sensitive material, various methods used when introducing the coupler represented by the general formula [I] of the present invention into the constituent layers are employed. Can be done using. For example, a method of dissolving in a high boiling point organic solvent and / or a low boiling point (30 to 150 ° C. at normal pressure) organic solvent and dispersing in a hydrophilic colloid medium, a polymer latex dispersion method, and the like can be applied.

The compound represented by the general formula (H) of the present invention is used in the same layer containing the coupler represented by the general formula [I] of the present invention to enhance the activation of the coupler. It suppresses the increase in fog that accompanies it, and provides high-quality and high-contrast images as well as good photographic properties with less fog. In addition, bleaching fog that occurs in the bleaching process after color development in the color developing process (particularly, 1,3-
The use of PDTA increases the bleaching fog), and suppresses the increase in yellow density that occurs in the uncolored part when the photosensitive material after color development processing is stored for a long time, and prevents these color stains, resulting in excellent image quality. Is to give. When the compound represented by the general formula (H) of the present invention is used in a non-photosensitive layer provided between two layers having different color sensitivities, the compound from the layer having different color sensitivities is used. It is possible to prevent unnecessary dyes from being generated due to the diffusion of the oxidized product of the developing agent, which exhibits a so-called color mixing prevention function and improves color reproducibility. Further, the compound represented by the general formula (H) of the present invention is applied to two or more layers of the coupler-containing layer of the present invention and a non-photosensitive layer provided between two layers having different color sensitivities. When used, all of those effects shown above can be exhibited, and the object of the present invention can be effectively and beautifully achieved.

In the present invention, in order to further improve the image quality of color reproduction, it is preferable to use a bleaching accelerator releasing compound in the layer containing the coupler represented by the general formula [I] of the present invention. Examples of the bleaching accelerator releasing compound include the compounds shown below, compound examples B-1 to B-24 described in JP-A-6-250356, JP-A-2-93454, and JP-A-63-214752. Gazette, the same 63-12
1844, 63-106749, and 61.
-201247, Research Disclosure
The compound described in No. 24241 can be applied.

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 used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing up to 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 No. 18716 (November 1979), p. 648,
Id. No. 307105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie et Phisique Photographique,
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emul)
sion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (V.
L. Zelikman, et al., Making and Coating Photograp
hic Emulsion, Focal Press, 1964) and the like.

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.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are RD No. 17643 and RD No. 17643.
18716 and No. 307105, and the relevant locations are summarized in the table below. The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, a grain size distribution,
Two or more kinds of emulsions having different characteristics of at least one of halogen composition, grain shape, and sensitivity can be mixed and used in the same layer. U.S. Pat.No.4,082,553.
It is preferable to apply the silver halide grains and the colloidal silver covered with the inside of the grains described in 9-214852 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 preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least the weight or the number of silver halide grains).
95% have a particle size within ± 40% of the average particle size)
It is preferred that

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 table below. 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 Page 876 Lubricant 8. Coating aid, Page 26-27 Page 650 Right column 875-876 Page Surfactant 9. Static page 27 Page 650 Right column 876-877 Inhibitor 10. Matting agent 878-879 Page

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); A-4 -6 of EP 456,257
3 (p. 134), A-4 -73, -75 (p. 139); M-4, -6 in EP 486,965
(Page 26), M-7 (page 27); EP-571,959A M-45 (page 19);
5-204106 (M-1) (page 6); JP-A-4-362631, paragraph 0237 M-
twenty two. 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), 34,3 of JP-A-4-43345.
5 (page 37), (I-1), (I-17) (pages 42 to 43); A coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. 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)
.

As the additives other than the coupler, the following are preferable. 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; Antistain agent: EP 298321A
Formulas (I) to (III) on page 4, lines 30 to 33, especially I-47, 72, III-1, 27
(Pages 24-48); Anti-fading agents: EP 298321A, A-6, 7, 20, 21,
23,24,25,26,30,37,40,42,48,63,90,92,94,164 (69 ~ 11
Pp. 8), US 5,122,444 columns 25-38 II-1 to III-23, especially III-10, EP 471347A pages 8-12 I-1 to III-4, especially II.
-2, US 5,139,931 columns 32-40 A-1 to 48, especially A-3
9,42; Materials that reduce the use of color-enhancing agents or color-mixing inhibitors: EP 411324A, pages 1-24, I-1 to II-15, 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 ~ (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13),
US 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-15 of JP-A-3-156450
A-1 to b-20 on page 18, especially a-1,12,18,27,35,36, b-5,27 to
Page 29, V-1 to 23, especially V-1, EP 445627A, Pages 33 to 55, F-
I-1 ~ F-II-43, especially FI-11, F-II-8, EP 457153A 17 ~
Page 28, III-1 to 36, especially III-1,3, WO 88/04794, 8 to 26
A microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular compounds D-1 to 87 (compounds 1 and 519306A represented by formulas (1) to (3)). (Pages 3 to 28), US 4,2
Compounds 1 to 22 represented by the formula (I) of 68,622 (columns 3 to
10), compounds (1) to (4) of the formula (I) 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. A color negative film is particularly preferable. Also, it is suitable for a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784.
Suitable supports that can be used in the present invention include, for example, the aforementioned R
D. Page 28 of No. 17643, Page 647 of No. 18716, from right column 6
It is described on page 48, left column, and page 879 of the same No. 307105. 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 has a total dry film thickness of 2 μm to 20 on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of 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. 17
Development can be carried out by a conventional method described on pages 28 to 29 of 643, 651 left column to right column of No. 18716, and pages 880 to 881 of No. 307105. Next, the processing solution for the color negative film used in the present invention will be described. The color developing solution used in the present invention is described in JP-A-4-2171.
The compounds described on page 9, upper right column, line 1 to page 11 lower left column, line 4 can be used. 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, 2-methyl-4- [N-
Ethyl-N- (4-hydroxybutyl) amino] aniline is preferred. These color developing agents are preferably used in the range of 0.01 to 0.08 mol per liter of the color developing solution, particularly preferably 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 in 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, the above JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, 16th page
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 reduce the replenishment amount by performing the reverse osmosis membrane treatment described in 55542, 3-121448, and 3-26030. In this case, the reverse osmosis membrane is preferably a low-pressure reverse osmosis membrane.

In the treatment of the present invention, it is particularly preferable to carry out the evaporation correction of the treatment liquid disclosed in the Technical Disclosure Bulletin of Japan Institute of Invention and Innovation, 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.

Next, the processing solution 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 preferably 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, etc. can be used. Co-deposited ferromagnetic iron oxides such as Co-deposited γFe ₂ O ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. In terms of specific surface area, S _BET is preferably 20 m ² / g or more,
30 m ² / g or more is particularly preferable. Saturation magnetization (σs) of ferromagnet
Is preferably 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, particularly preferably 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, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032.
In addition, the surface of the inorganic particles described in JP-A-4-259911 and 5-81652 is
Magnetic particles coated with an organic substance can also be used.

The binder used in 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, etc. are 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.

Hereinafter, the structure of a preferable photographic light-sensitive material package (hereinafter, also referred to as "photographic film cartridge") 100 will be described with reference to the drawings. 1 is an exploded perspective view of the photographic film cartridge, FIG. 2 is a view of the photographic film cartridge viewed from the radial direction, and FIG. 3 is a view of the photographic film cartridge viewed from the radial direction at a position different from FIG. The photographic film cartridge 100 includes a cartridge body 101 in which a spool 103 around which a photographic photosensitive material (photo film) 102 is wound is rotatably housed.
A cartridge label 104 is adhered to the outer periphery of 1.
The cartridge body (patrone body) 101 is composed of upper and lower cases 105 and 106 which are two molded parts.

An upper case 105 having a gate 150,
Photo film 1 on the front side joint with the lower case 106
A film delivery port 107 (passage) for delivering 02 is formed. A lid member 108 for preventing light from entering there is behind the film delivery port 107.
And a separation claw 109 which is arranged at the back of the separation film and separates the tip of the photographic film 102. The lid member 108 has key grooves 110,
111 is formed, and the keyway 11 is formed when loaded in the camera.
The opening / closing drive shaft on the camera side that engages with 0 and 111 is rotated between a closed position that closes the film feed opening 107 and an open position that allows entry and exit of the photographic film. FIG. 5 shows a state in which the lock pawl 144 and the lid member 108 are engaged with each other and the lid member is locked at the closed position.

The spool 103 comprises a pair of lip flanges 113, 1 on the inner sides of the spool shaft 112, respectively.
14 is attached, and a data disk is provided on the outside of one flange 113. The other flange 1
A use display member 123 is attached to the outer side of 14. A data label is attached to the data disk 115. A pair of flange engaging portions 1 with which the spool shaft 112, the data disk 115, and the respective flanges 113 and 114 are engaged.
17, 118, slit 11 for locking the rear end of the photographic film
9 and the use display member supporting portion 120 are formed integrally with each other, and when the spool 10 is mounted on the camera,
The drive shaft on the camera side is engaged with the key grooves 121 and 122 on the key holes provided at both ends of the drive shaft 3, and is rotated by the rotation of the drive shaft.

The use display member 123 includes a bearing portion 12
The four ratchet pawls 125, the gear 126, and the use display plate 127 are integrally formed, and these rotate integrally with the spool shaft 112.

The inside of the photographic film cartridge 100 is
A spool lock 128 is housed so as to mesh with the gear 126. This spool lock 128 is a lid member 1.
When 08 is in the closed position, the gear 126 is engaged to lock the rotation of the spool shaft 112, prevent careless feeding of the photographic film 102, and cover member 108.
When is in the open position, it disengages from the gear 126.

The pair of flanges 113 and 114 are formed of a plastic material and have a thin cup-shaped cross section. The cup-shaped bottom has a flange engaging portion 117,
Round holes 129 and 130 are rotatably engaged with 118, respectively. Also, the cup-shaped opening edge 13
1, 132 are arranged to face each other when attached to the spool shaft 112, and wrap around the outermost ends of the photographic film 102 wound between them (see FIG. 6). The opening edge portions 131 and 132 allow the rotation of the spool 103 to be transmitted to the outermost periphery of the photographic film 102 and prevent the film roll 142 from being loosened.

The flange 114 is formed with four holes 133 at a predetermined pitch so as to surround the round hole 130. These holes 133 are provided with a display member 123 for use when the spool shaft 112 rotates in the photo film feeding direction.
Ratchet claw 125 of is engaged. Ratchet claw 125
Transmits the rotation of the spool shaft 112 to the flange 114 when engaged with the hole 133, and when the spool shaft 112 rotates in the photo film winding direction, the ratchet claw 125 of the use indicating member 123 causes the hole 133 to rotate. Therefore, the rotation of the spool shaft 112 is not transmitted to the flange 114.

When the photographic film 102 is fed, the spool 103 is rotated in the film feeding direction. When the spool 103 is rotated in the film feeding direction, the tip of the photographic film 102 is separated by the separation claw 10.
9 and is separated from the part wound inside the leading edge of the photographic film. When the spool 103 is subsequently rotated, since the pair of thin flanges 113 and 114 has elasticity, the pair of flanges 113 and 114 are pushed outward by the separated film tips. The leading edge of the photographic film (143 in FIG. 3) released from the wrapping is delivered to the outside of the photographic film cartridge 100 through the film delivery port. Further, when the spool shaft 112 rotates in the photo film winding direction (the direction opposite to the photo film feeding direction), the flanges 113 and 114 do not rotate integrally with the spool shaft 112. Therefore, the photographic film 102
Since the flanges 113 and 114 do not rotate when the film is wound, a slip occurs between the opening edge portions 131 and 132 and the photographic film 102, and the photographic film 102.
Slides under the opening edges 131, 132 of the flanges to wrap the photographic film.

The data disk 115 has a large-diameter fan-shaped portion 1
34 and a notch portion 135. The barcode label 116 has a shape similar to that of the data disc 115 and is attached to the data disc.

A bar code is printed on the bar code label 116 and represents various information such as the type of the photo film 102 to be stored. This information is obtained when the spool 103 is rotated in the film feeding direction.
As shown in FIG. 5, it is read by a reading sensor provided on the camera side through an opening 136 formed on one side surface of the upper case 105 to calculate an exposure value and count the number of exposures of stored photo films. Used.

In this photo film cartridge 100,
Since even the leading edge of the photographic film 102 is stored, it is indistinguishable from the external appearance whether the unexposed photographic film or the exposed photographic film is stored. Therefore, in order to prevent the photographic film cartridge 100 containing the exposed photographic film from being reloaded into the camera and taking pictures, a post-loading prevention opening 137 is formed on one side surface of the lower case 106. There is. This one side surface is a side that is inserted toward the cartridge chamber of the camera, and a lever that enters the opening 137 is provided in the cartridge chamber.

The photographic film cartridge 100 stores the unexposed photographic film so that the large-diameter fan-shaped portion 134 is exposed in the opening 137 when the exposed photographic film is stored. If so, the stop position of the spool 103 is controlled by the drive shaft on the camera side so that the large-diameter fan-shaped portion 134 is not exposed in the opening 137. Therefore, by detecting the amount of movement of the lever, the camera side can discriminate between the exposed and unexposed photographic film.

Furthermore, in order to allow the user to understand the appearance, the photo film cartridge 100 is
As shown in FIG. 4, on the other side surface (the side surface opposite to the side surface on which the openings 136 and 137 are provided), an opening 138 for displaying the usage state when the unexposed photo film is stored, a part thereof is photographed. When the photographic film is stored, the usage status display opening 139, when the exposed photo film that has been photographed on all is stored, the usage status display opening 140, and when the developed photographic film is stored Of the four use status display openings 138 to 141 are formed by exposing the use display plate 127 located in the back by controlling the stop position of the spool 103. The usage status of the film is displayed.

Further, the present cartridge 100 is provided with a sensitivity detecting notch 145 used for detecting the sensitivity of the stored photographic film 102. This is a notch for detecting sensitivity with an inexpensive camera that does not have a bar code reader that reads the bar code written on the bar code label. When the sensitivity detecting notch 145 is provided as shown in FIG. 5, the stored photographic film 102 is IS.
The O sensitivity is 400 or more, and the ISO sensitivity is 400 or less when there is no notch.

Further, the present cartridge 100 is provided with a developed display tab showing whether the stored photographic film 102 has been developed or not. As shown in FIG.
The tab 147 is provided in an opening 146 provided on one side surface of the cartridge 100, and when the tab 147 is broken off, it means that the stored photographic film 102 has been developed.

Next, a typical example of the manufacturing method of the cartridge 100 of the present invention will be specifically described. Upper case / lower case 1
05, 106, the spool 103, and the lid member 108,
High-impact polystyrene resin (Denkastyrol HI-R-Q manufactured by Denki Kagaku Kogyo) is added with 1.0% by weight of carbon black (Mitsubishi Carbon Black # 950 manufactured by Mitsubishi Chemical) for imparting light-shielding properties, and lubricity. Silicone oil for use (Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone KF96H-viscosity 30,000 cs) is molded by injection molding using a resin kneaded with 1.5% by weight. The use indication member 123 is made by injection molding using a resin obtained by kneading the above-mentioned high impact polystyrene resin with 0.01% by weight of the above carbon black and 3.5% by weight of titanium oxide (CR60-2 manufactured by Ishihara Sangyo). Mold.

The flanges 113 and 114 are formed by a vacuum / pneumatic method using a film having a thickness of 150 μm made from a polymer alloy of polystyrene resin and polyphenylene ether resin (Zylon X9101 manufactured by Asahi Kasei).

The patrone label 104 has a thickness of 50.
A coating for imparting printability is provided on one side of a polystyrene film containing a white pigment having a thickness of μm, an adhesive is attached to the back side thereof, and a release paper is attached to the release label to prepare an adhesive label stock. As shown in FIG. 7, on the surface of the original fabric,
Patrone ID number printing space written in numbers 15
1. A manufacturer name, a product name, a film type / sensitivity / the number of exposures, a cautionary note, and a print space 152 for a product type for printing a memo field to be filled by the user, and a bar code print space 153. First, a printing space such as a product type is printed, then half-cut processing is performed, and thereafter, a barcode and a Patrone ID number are printed to create. The bar code contains the manufacturer's name, production lot, production date, type of photo film stored, sensitivity, number of exposures,
Also, the Patrone ID number and the like are encoded and printed. The cartridge ID number is a unique number attached to each cartridge.

The bar code label 116 has a thickness of 50 μm.
A transparent vapor deposition polystyrene film with a thickness of about 400 Å is provided on one side of the transparent vapor deposition film, and an adhesive label is attached on top of it to create an adhesive label with release paper, and a bar on the opposite side of the aluminum vapor deposition layer. After printing the code, half cut the outer peripheral part, and then punch out the center to create.

[0100]

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-mentioned 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.

[0104]

Embedded image

4) Coating of Sensitive Material Layer Next, each layer having the following composition was coated on the side opposite to the back layer obtained above to prepare a color negative film. This is designated as Sample 101. The number corresponding to each component is g / m ²
The coating amount is shown in units, and for silver halide, the coating amount in terms of silver is shown.

First layer (gelatin layer) Gelatin 3.00 Second layer (emulsion layer) Silver iodobromide emulsion (cubic, average AgI content 2.0 mol%, shell shell 1.23 high iodine double structure, grain Coefficient of variation related to diameter 10%, average particle diameter (sphere equivalent diameter 0.25 μm) Comparative coupler (1) 1.53 Tricresyl phosphate (TCP) / dibutyl phthalate 0.92 (DBP) (2/1 weight ratio) Gelatin 2.25 Third layer (protective layer) Gelatin 2.50 1-Oxy-3,5-dichloro-s-triazine sodium 0.18

Then, the following samples were prepared. Samples 102 and 103 The comparative coupler (1) used in Sample 101 was replaced with Sample 10
2 is the comparative coupler (2), Sample 103 is the coupler Y-4 represented by the general formula [I] of the present invention in equimolar amounts, and the mixed high boiling point organic solvent of TCP / DBP has a weight ratio to the coupler. Same weight ratio as sample 101 (0.6)
A sample was prepared by adjusting so that Samples 104 to 106 Comparative compound (1) was used in the second emulsion layer of Samples 101 to 103.
Was added to give a coating amount of 0.054 g / m ² . This comparative compound (1) was used as a mixture with a coupler. Samples 107 to 109 The comparative compound (1) used in the above samples 104 to 106 was replaced with the comparative compound (2) in an equimolar amount, and prepared in the same manner. Samples 110 to 112 The comparative compound (1) used in Samples 104 to 106 was prepared by substituting the compound H-24 represented by the general formula (H) of the present invention in an equimolar amount. Comparative couplers (1) and (2) and comparative compounds (1) and (2) used in the preparation of the above sample are shown in Chemical formula 25.

[0108]

Embedded image

Further, the following samples were prepared. Samples 113 to 121 The coupler Y-4 of the present invention used in Sample 112 was replaced with another coupler of the present invention in the same molar amount as shown in Table 1, and the weight ratio of the mixed high-boiling organic solvent to the coupler was the same. Then, a sample was prepared. Samples 122 to 129 The compounds H-24 represented by the general formula (H) of the present invention used in Sample 112 were replaced by other compounds of the present invention in equimolar amounts as shown in Table 1. Sample 130 Sample 112 was prepared by adding the compound H-28 of the present invention to the first layer so that the coating amount was 0.052 g / m ² .
The mixed high boiling point organic solvent was added as a dispersion in which the weight ratio to the compound was 2.0 and the mixture was emulsified and dispersed. Sample 131 Similarly, in the first layer of Sample 112, the coupler Y-10 of the present invention was used.
Was added so that the coating amount was 0.015 g / m ² . DBP was used as the high-boiling organic solvent for the coupler, and it was added so that the weight ratio to the coupler was 1.0, and used as an emulsified dispersion.

[0110]

[Table 1]

These samples thus prepared were examined for the following performance after aging for 7 days at 25 ° C. and 60% relative humidity. (1) Photographic property Using a wedge for sensitometry, a constant light amount of white light exposure was performed, and the density of a yellow color image obtained by performing the following color development processing was measured. The logarithmic value of the reciprocal of the exposure amount that gives the density of the minimum density value (fog) +0.5 was determined and used as the sensitivity. Taking the value of sample 101 as a reference, the difference from each sample (Δ
S) was calculated. The larger the value, the higher the sensitivity and the more preferable it is. (2) Change in minimum density value with time after color development processing Each unexposed sample was subjected to the following color development processing, and its B density was measured, and then these samples were subjected to 35 ° C. and 65% relative humidity.
The sample was stored for 50 days under the above conditions, the B concentration was measured again, and the difference between the concentration value after aging and the concentration value before aging (Δ
Dmin) was calculated. The larger the value, the more the minimum density value increases over time, which is disadvantageous in color reproduction, color correction during color printing, printing time, and the like. (3) Bleaching fog While each sample was left unexposed, one set was subjected to color development processing as described below, followed by color development, followed by washing with water for 10 seconds, and another set was subjected to color development followed by 2% acetic acid aqueous solution for 10 seconds. and, the process will perform exactly the color development processing in the same post, the resulting sample was respectively measured B concentration, the concentration difference between the mere washing treatment and a 2% aqueous acetic acid solution between the same samples ([Delta] D _BS) I asked. The larger this density difference is, the more the color developing agent taken into the sample during color development during bleaching is brought in,
It shows whether the developing agent undergoes oxidation in the bleaching oxidation bath to form a color with the coupler, which is called bleaching fog (post-coloring) and shows an undesired increase in B density. Such an increase in B concentration brings about the same disadvantage as the above (2). The color development processing used in (1) to (3) is shown below. The results are summarized in Table 1.

Each processing was performed by using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd., and a photograph of Fuji Color Negative, Super Ace 400 (manufactured by Fuji Photo Film Co., Ltd.) was taken by a camera for 1 m ^{2 a} day. The following treatments were performed for 15 days each (running treatment), and then the following treatments were performed. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. 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) Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 20 ml 17 liter Bleach 50 seconds 38.0 ° C 5 ml 5 liter Fixing (1) 50 seconds 38.0 ° C -5 liter Fixing (2) 50 seconds 38.0 ℃ 8 ml 5 liters Water wash 30 seconds 38.0 ℃ 17 ml 3.5 liters Stable (1) 20 seconds 38.0 ℃ −3 liters Stable (2) 20 seconds 38.0 ℃ 15 milliliters 3 liters Dry 1 minute 30 60 ° C / sec * Replenishment amount per 35 m width of photosensitive material 1.1 m (equivalent to 24 Ex. 1) Stabilizer is countercurrent method from (2) to (1), and overflow liquid of washing water is fixed (2) ) Was introduced. The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 2.
It was 5 ml, 2.0 ml, and 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 cm ^{2 with the} color developer,
The bleaching solution had a volume of 120 cm ² , and the other processing solutions had a volume of approximately 100 cm 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 Potassium carbonate 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 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide 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 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 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 ammonia water 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 0.2 (Average degree of polymerization 10) Disodium ethylenediaminetetraacetic acid Salt 0.05 1,2,4-triazol 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 the table, Samples 112 to 131 of the constitution of the present invention using the compound represented by the general formula [I] of the present invention and the compound represented by the general formula (H) are more photographic than the comparative sample. Provides high sensitivity, the density increase of the uncolored part is small even after aging of the sample after color development processing, and there is little fog during bleaching during color development processing. It shows reproducibility and achieves the object of the present invention. In this example, the increase in the B concentration in the uncolored portion that occurred when the sample after color development processing was aged was due to the fact that the developing agent remaining in the sample after color development processing was subjected to air oxidation during the time and no color developed. It is considered that a dye is formed by a coupling reaction with a coupler existing in a part. Further, the difference between washing with water before the bleaching bath and treatment with a dilute acetic acid aqueous solution causes the developing agent incorporated into the sample during the color developing treatment to produce a dye by the oxidation of the bleaching bath and increase the B concentration. However, this increase in density is small. This is probably because there is little difference between the samples in the amount including the coupler oil droplet of the developing agent in each sample (because it is high if the developing agent is not incorporated in the sample film and the oil droplets. This is because the color density cannot be obtained), and it is considered that the incorporated developing agent easily elutes outside the system such as oil droplets or in the sample film.

Example 2 Sample 201, which is a multilayer color light-sensitive material having the following compositions, was prepared on the surface of the support used in Example 1 on the side opposite to the back layer. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there is more than one utility, only one of them is listed as a representative. UV; UV absorber, Solv; high boiling organic solvent, Ex
F: dye, ExS: sensitizing dye, ExC: cyan coupler, ExM: magenta coupler, ExY: yellow coupler, Cpd;

1st layer (antihalation layer) Black colloidal silver 0.19 Gelatin 1.64 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 1.0 × 10 ^-2 ExF -2 4.0 x 10 ^-2 ExF-3 5.0 x 10 ^-3 ExM-3 0.11 ExC-7 9.4 x 10 ^-2 Cpd-5 1.0 x 10 ^-3 Solv-1 0.16 Solv-2 0.10

Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount of silver 0.25 Silver iodobromide emulsion B Coating amount of 0.40 Gelatin 1.53 ExS-1 6.5 × 10 ^-4 ExS-2 3.6 × 10 ^-4 ExS-5 6.2 x 10 ^-4 ExS-7 4.1 x 10 ^-6 ExC-1 1.6 x 10 ^-1 ExC-4 7.7 x 10 ^-2 ExC-5 1.1 x 10 ^-1 ExC-6 3.7 x 10 ^-2 ExC-7 3.7 × 10 ^-2 ExC-9 5.0 × 10 ^-3 Cpd-4 6.7 × 10 ^-2 Solv-1 0.13

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Coating amount 0.78 Gelatin 0.95 ExS-1 4.3 × 10 ^-4 ExS-2 2.4 × 10 ^-4 ExS-5 4.1 × 10 ^-4 ExS-7 4.3 x 10 ^-6 ExC-1 1.1 x 10 ^-1 ExC-4 3.9 x 10 ^-2 ExC-5 7.2 x 10 ^-2 ExC-6 3.2 x 10 ^-2 ExC-7 2.6 x 10 ^-2 ExC- 9 1.2 x 10 ^-2 Cpd-4 2.8 x 10 ^-2 Solv-1 0.08

Fourth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Coating amount 0.98 Gelatin 0.82 ExS-1 3.6 × 10 ^-4 ExS-2 2.0 × 10 ^-4 ExS-5 3.4 × 10 ^-4 ExS-7 1.4x10 ^-5 ExC-1 7.2x10 ^-2 ExC-4 2.2x10 ^-2 ExC-7 1.2x10 ^-2 ExC-8 1.0x10 ^-2 ExC-9 2.3x10 ^-2 Cpd- 4 3.2 x 10 ^-3 Cpd-7 2.0 x 10 ^-3 Solv-1 0.10 Solv-2 0.06

Fifth Layer (Intermediate Layer) Gelatin 0.92 Cpd-1 0.12 Cpd-8 4.0 × 10 ^-3 Polyethyl acrylate latex 4.1 × 10 ^-2 Solv-1 6.0 × 10 ^-2

Sixth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion A Coating amount of silver 0.07 Silver iodobromide emulsion E Coating amount of 0.15 Gelatin 0.73 ExS-4 1.28 × 10 ^-5 ExS-5 2.1 × 10 ^{-4 ExS-8 1.2 × 10 -4} ExM-1 0.19 ExM-3 9.7 × 10 -2 ExY-1 1.3 × 10 -2 Solv-1 0.27 Solv-3 7.0 × 10 -3

Seventh layer (medium sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion B Coating amount of silver 0.12 Silver iodobromide emulsion F Coating amount of 0.13 Gelatin 0.30 ExS-4 8.5 × 10 ^-4 ExS-5 1.4 × 10 ^-4 ExS-8 8.3 x 10 ^-5 ExM-1 6.9 x 10 ^-2 ExM-7 2.9 x 10 ^-2 ExY-1 1.1 x 10 ^-2 Solv-1 0.076 Solv-3 1.8 x 10 ^-2

Eighth layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion D Coating amount 0.76 Gelatin 0.69 ExS-4 7.1 × 10 ^-4 ExS-5 1.4 × 10 ^-4 ExS-8 4.6 × 10 ^-5 ExM-1 4.8 × 10 ^-2 ExM-3 1.8 × 10 ^-2 ExM-8 5.0 × 10 ^-3 ExY-1 4.0 × 10 ^-2 ExC-1 9.0 × 10 ^-3 ExC-4 1.2 × 10 ^-3 Cpd- 6 2.0 x 10 ^-3 Solv-1 0.12

Ninth layer (intermediate layer) Gelatin 0.66 Cpd-1 2.0 × 10 ^-2 Polyethyl acrylate latex 1.4 × 10 ^-2 Solv-1 1.0 × 10 ^-2 Tenth layer (donor layer having a multi-layer effect on the red-sensitive layer) ) Silver iodobromide emulsion A coated silver amount 0.12 silver iodobromide emulsion G coated silver amount 0.52 silver iodobromide emulsion H coated silver amount 0.20 gelatin 1.58 ExS-3 8.5 × 10 ^-4 ExS-4 1.5 × 10 ^-4 ExM -0.22 Cpd-7 9.0x10 ^-3 Solv-1 0.67 11th layer (yellow filter layer) Yellow colloidal silver 9.2x10 ^-2 Gelatin 0.83 Cpd-5 1.0x10 ^-3 Solv-1 0.070

Twelfth layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion I Coating amount of silver 0.25 Gelatin 0.92 ExS-6 9.0 × 10 ^-4 ExY-6 8.5 × 10 ^-2 ExY-2 5.5 × 10 ^-3 ExY-3 (comparative coupler (2)) 0.40 ExC-1 5.8 × 10 ^-2 ExC-9 3.0 × 10 ^-2 ExC-11 1.0 × 10 ^-2 Solv-1 0.20

Thirteenth layer (medium-sensitive blue-sensitive emulsion layer) Silver iodobromide emulsion J Coating amount 0.30 Silver iodobromide emulsion K Coating silver amount 0.15 Gelatin 2.49 ExS-6 9.0 × 10 ^-4 ExY-6 3.9 × 10 ^-2 ExY-4 0.23 ExY-3 (comparative coupler (2)) 1.05 ExC-10 0.19 ExC-9 3.0 x 10 ^-2 ExC-11 1.0 x 10 ^-2 Cpd-7 4.0 x 10 ^-3 Solv-1 0.53

14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Coating amount 0.24 Gelatin 0.31 ExS-6 6.3 × 10 ^-4 ExY-3 (comparative coupler (2)) 0.10 ExY-4 2.0 × 10 ^-2 ExC-11 0.5 x 10 ^-2 Solv-1 0.06 Fifteenth layer (first protective layer) Fine grain silver iodobromide emulsion M Coating amount 0.60 Gelatin 1.14 UV-4 0.11 UV-5 0.18 Cpd-3 0.10 Solv -1 2.0 x 10 ^-2 Polyethyl acrylate latex 9.0 x 10 ^-2

16th layer (second protective layer) Gelatin 0.76 B-1 (diameter 2.0 μm) 8.0 × 10 ^-2 B-2 (diameter 2.0 μm) 8.0 × 10 ^-2 B-3 2.0 × 10 ^-2 W- 5 2.0 x 10 ^-2 H-1 0.34

In addition to the above, the samples thus prepared include
1,2-Benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. In addition, each layer has appropriate storage properties, processability, pressure resistance, mildew / bacterial resistance,
In order to improve the antistatic property and coating property, W-1 to W-
6, B-1 to B-6, F-1 to F-16, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

[0135]

[Table 2]

In Table 1, (1) Emulsions H to L were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) By using a high voltage electron microscope, dislocation lines as described in JP-A-3-237450 can be observed in the tabular grains. (5) Emulsions A to L are BH Carroll, Photographic Scien
Ce and Engineering, 24, 265 (1980), iridium is contained inside the particles.

[0137]

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Then, the following samples were prepared. Sample 202 Coupler E used in the 12th to 14th layers of Sample 201
xY-3 is a coupler Y represented by the general formula [I] of the present invention.
A sample was prepared by substituting equimolar amount of -5 and adjusting Solv-1 of the high boiling point organic solvent so that the weight ratio to the coupler was the same. Samples 203 and 204 The comparative compound (1) used in Example 1 was used in the 11th to 14th layers of Samples 201 and 202, and 7.5 × 1 in the 11th layer.
0 ^-2 g / m ^2, the twelfth layer ^{3.8 × 10 -2 g / m 2} , 13
3.8 × 10 ⁻³ g / m ² for the layer and 7.6 × 10 ^{−3 for} the 14th layer
It was prepared by adding so that the coating amount was g / m ² . Samples 205 and 206 The comparative compound (1) used in the 11th to 14th layers of Samples 203 and 204 was added to the compound H-24 represented by the general formula (H) of the present invention, and tripled in the 11th layer. The moles and the twelfth to fourteenth layers were produced by substituting twice the molar amount. Samples 207 to 209 The coupler Y-5 of the present invention used in the twelfth to fourteenth layers of Sample 206 was replaced with another coupler of the present invention as shown in Table 3, and the weight ratio of Solv-1 to the coupler was changed. Samples were prepared in the same manner as the above samples. Samples 210 to 212 The compound H-24 of the present invention used in the 11th to 14th layers of the sample 206 was added to other compounds of the present invention as shown in Table 3 and also to the 12th to 14th layers. The coupler Y-5 of the present invention used was prepared by substituting the other couplers of the present invention shown in Table 3 in an equimolar amount. Regarding the coupler, the weight ratio of Solv-1 used was the same as above.

[0154]

[Table 3]

The light-sensitive material manufactured as described above is used for 24 mm
The photosensitive material is cut to a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. A set in which these two sets were provided at intervals of 32 mm was prepared and housed in the plastic film cartridge described in FIGS. 1 to 7 described above. For this sample, an FM signal was sent from the coated surface side of the magnetic recording layer at a feed speed of 1,000 / s during the above-mentioned perforation of the photosensitive material by using a head having a head gap of 5 μm and a turn count of 2,000. Recorded. These were stored at 25 ° C. and 55% relative humidity for 3 days, and the following performances were examined.

(1) Photographic property The light-sensitive material was cut into a required length, and each sample was exposed to a certain amount of white light using a wedge for sensitometry, and the color development processing described in Example 1 was performed. B of the obtained color image
The concentration is measured, the minimum concentration value of the B concentration is read from the characteristic curve, and the difference (Δfog) with reference to the sample 201
I asked. The larger the value with a minus sign,
It has a low fog density and exhibits favorable photographic properties. (2) Density change of uncolored portion with time after color development processing The photosensitive material was taken out from the cartridge, and the sample of the entire length thereof was subjected to the color development processing described in Example 1 without exposure, and the B concentration of each sample. Read the value. After that, these processed films are rewound into the cartridge,
These light-sensitive materials were left in a car under the scorching sun in midsummer for 5 days. The temperature in the vehicle at this time was a temperature history in the range of 25 ° C to 75 ° C, and the relative humidity was also in the range of 45 to 80%. This temperature / humidity range is something that is always experienced and not particularly harsh. After being left in the car, the photosensitive material was taken out from the cartridge and the B density was measured again to read the density value. In this concentration value, a slight concentration pattern was observed between the winding core side and the outside, and the winding core side gave a high concentration. The difference (ΔDmin) between the density value on the winding core side and the density value before aging was determined. The smaller the value, the smaller the increase in the density of the uncolored portion over time, which is preferable in terms of color reproducibility and the like as in Example 1. (3) Color Mixing The light-sensitive material was cut to a required length, exposed to light by attaching a green filter to the front surface of the sensitometric wedge, and G and B densities of the obtained magenta image were measured.
The characteristic curve was obtained on the same chart. The minimum density value on the curve measured at the same B density is read by reading the density value of the curve measured at the same B density of the exposure amount that gives the minimum density on the curve measured by the G density of this characteristic curve +2.0. The subtracted value was determined for each sample. Regarding these values, the difference (ΔB _G ) of each sample was calculated based on the sample 201. The larger the value with a minus sign,
It shows that there is little color mixture, which is preferable for color reproduction. Table 3 shows the results of these (1) to (3).

From the table, the sample of the present invention satisfying the constitution of the present invention gives good photographic property with less fog, and the increase in B density of the uncolored portion with the lapse of time after color development treatment is the same as in Example 1. It is clear that the color reproducibility is small and the B density component in the magenta color image is small to give high color purity. From these results, it can be seen that the sample satisfying the constitution of the present invention successfully achieves the object of the present invention. Regarding the color mixture, the color developing agent is oxidized by color development by being exposed to green light, and the oxidant diffuses to reach the adjacent blue-sensitive layer and undergoes a coupling reaction with the coupler in the layer. It is thought that it produced yellow dye,
It exhibits excellent color reproducibility by incorporating the original excellent spectral absorption characteristics of the coupler of the present invention.

EXAMPLE 3 The support used in Example 2 was replaced with a cellulose triacetate support with undercoat on both sides, and the sample 201 of Example 2 was replaced.
To 216, the constituent layers having the same structure as that of
12 is created and the same performance evaluation as in the embodiment is performed,
It can be confirmed that the same results as in Example 2 can be obtained and the object of the present invention can be achieved.

[0159]

According to the present invention, at least one light-sensitive silver halide emulsion layer and at least one layer of a color light-sensitive material having a non-photosensitive property contain a coupler represented by the general formula [I]. In addition, the color light-sensitive material containing the non-color-forming and diffusion-resistant compound represented by the general formula (H) exhibits good photographic properties with high fog and little fog, and is aged after color development processing. However, it is possible to provide a silver halide color photographic light-sensitive material having a small increase in density, a small amount of bleach stain, a small amount of color mixture in a multi-layer sample, and little color contamination or color mixture and excellent color reproducibility.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view of a photographic light-sensitive material package (photographic film cartridge) according to one embodiment of the present invention.

FIG. 2 is a diagram of the photographic light-sensitive material package as viewed from a radial direction.

FIG. 3 is a view of the photographic light-sensitive material package viewed from a radial direction at a position different from that in FIG.

FIG. 4 is a view of the photographic light-sensitive material package as viewed from one side in the axial direction thereof.

FIG. 5 is a view of the photographic light-sensitive material package as seen from the other axial direction.

FIG. 6 is a sectional view of the photographic light-sensitive material package cut along the axial direction.

FIG. 7 is a diagram showing an adhesive label stock sheet with release paper.

[Explanation of symbols]

 100 Photo Film Patrone 101 Patrone Main Body 102 Photo Film 103 Spool 104 Patrone Label 105 Upper Case 106 Lower Case 107 Film Feed Out Port 108 Lid Member 109 Separation Claw 110 Key Groove 111 Key Groove 112 Spool Shaft 113 Flange 114 Flange 115 Data Disc 116 Bar Code Label 117 Flange engaging portion 118 Flange engaging portion 119 Slit 120 Use display member support portion 121 Key groove 122 Key groove 123 Use display member 124 Bearing portion 125 Ratchet pawl 126 Gear 127 Display plate 128 Spool lock 129 Round hole 130 Round hole 131 Opening edge 132 Opening edge 133 Hole 134 Large-diameter fan-shaped portion 135 Notch 136 Opening 137 Opening 138 Displaying opening 139 Table Display opening 140 Display opening 141 Display opening 142 Film roll 143 Film tip 144 Rock paw 145 Sensitivity detection notch 146 Opening 147 Developed display tab 150 Gate 151 ID number printing space 152 Variety printing space 153 Bar code printing space

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 7/392 G03C 7/392 A

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive layer on a support, each containing a coupler represented by the general formula [I], A silver halide color photographic light-sensitive material containing a non-color forming and diffusion resistant compound represented by formula (H). Embedded image In the general formula [I], R ₁ is a tertiary alkyl group, R ₂
Is a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an alkylsulfonyloxy group, or a cycloalkyl group, R ₃ is an alkoxycarbonyl group, or an alkylsulfonyloxy group, R ₄ is a halogen atom,
An alkyl group, an alkoxy group, a carbonamido group, or a sulfonamide group, m is an integer of 0 to 2, R ₅ and R ₆ are each independently a hydrogen atom or an alkyl group, X is an oxygen atom, a sulfur atom, Or represents an imino group. Embedded image In the general formula (H), X represents —N (R ¹ ) R ³ or —O
Represents R ⁴ , wherein R ¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic residue, and R ³ and R ⁴ represent a hydrogen atom or a group which is removed under alkaline conditions. R ² is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a nitro group or a hydrazino group, and X and R ² may be linked to form a ring. R ⁵ represents a hydrogen atom, an alkyl group or a group removed under alkaline conditions. R ¹ , R ² or R
Two or more formulas (H) may be bonded to each other at the moiety ⁵ to form an oligomer or polymer. G is -CO-, -COC
_{O -, - SO 2 -,} - SO -, - CON (R 6) -, -
^{COO -, - COCON (R 7} ) -, - COCOO-,
^{-PO (R 8) -, -} PO (OR 9) -, - PO (OR
^{10) O -, - (C} = S) - or represents a iminomethylene group, wherein R ^6, R ⁷ is a hydrogen atom, an alkyl group or an aryl ^{group, R 8, R 9, R} 10 is an alkyl group or It is an aryl group. m is 0, 1 or 2, and when 2 is G, they may be the same or different.