EP0750225B1

EP0750225B1 - Use of hydroxamic acid derivatives for reducing the amount of residual sensitizing dyes after development processing

Info

Publication number: EP0750225B1
Application number: EP19960109407
Authority: EP
Inventors: Yoshio C/O Fuji Photo Film Co. Ltd. Ishii; Yousuke c/o Fuji Photo Film Co. Ltd. Miyashita; Hisashi C/O Fuji Photo Film Co. Ltd. Mikoshiba
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1995-06-12
Filing date: 1996-06-12
Publication date: 2000-10-04
Anticipated expiration: 2016-06-12
Also published as: DE69610530T2; DE69610530D1; EP0750225A1

Description

FIELD OF THE INVENTION

This invention relates to a silver halide color photographic material. More particularly, it relates to a silver halide color photographic material which has a reduced amount of sensitizing dyes remaining after development processing and undergoes little variation of photographic properties with time after exposure till development processing.

BACKGROUND OF THE INVENTION

Silver halide color photographic materials sometimes suffer from color stains due to sensitizing dyes remaining after development processing. In particular, in the system where tabular grains having a high aspect ratio are used, and sensitizing dyes are used in a photographic material in an increased amount to achieve high sensitivity of the photographic material, or where the processing time is reduced for for rapid processing, the amount of residual sensitizing dyes increase.
If residual sensitizing dyes increase, the light-sensitive material tends to suffer from large variation of the minimum density after development processing, or the light-sensitive material shows unevenness when, after it is processed, irradiated with light to optically read the image information. It has therefore been demanded to solve these problems.
U.S. Patents 5,188,926 and 5,192,646 describe that color stains due to residual sensitizing dyes after development processing particularly increase in the presence of couplers having a phenol group or other strongly hydrogen bond-donating groups and propose to reduce the residual sensitizing dyes by using a carbonamide solvent or a sulfoxide solvent for dispersing cyan-dye forming couplers, such as phenol couplers and naphthol couplers.
Although use of a carbonamide solvent or a sulfoxide solvent is effective to reduce color stains due to residual sensitizing dyes, it sometimes results in increased variation of photographic properties with time after exposure (photographing) till development processing. Therefore, further improvement has been still awaited.
Where sensitizing dyes are used in large quantities or where the processing time is shortened, further reduction of residual sensitizing dyes has been demanded.
U.S. Patent 4,330,606 discloses improvement of color fading by light by using substituted hydroxylamines, a part of which compounds are included in the compounds of the present invention. However, the U.S. patent is to improve photostability of indophenol, indoaniline or azomethine dyes produced on color development, having no mention nor implication of reduction in residual sensitizing dyes. In this aspect, the present invention differs from U.S. Patent 4,330,606.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide a silver halide color photographic material which has a reduced amount of sensitizing dyes remaining after development processing and undergoes little variation of photographic properties with time after exposure (photographing) till development processing.
It has now been found that the above object is accomplished by the use of a compound represented by formula (I) for reducing residual sensitizing dyes after development processing of a silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer, which comprises incorporating a compound represented by formula (I):
wherein R¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; R² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic group,
into said silver halide color photographic material.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is further described below in detail.
The compounds represented by formula (I) (hereinafter referred to as the compound(s) (I)) are explained in detail.
When R¹ in formula (I) is a substituted or unsubstituted alkyl group, the alkyl group preferably contains 1 to 30 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the alkyl group are methyl, ethyl, sec-butyl, t-octyl, benzyl, cyclohexyl, chloromethyl, dimethylaminomethyl, n-heptyl, n-undecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, trifluoromethyl, 3,3,3-trichloropropyl, and methoxycarbonylmethyl groups.
Substituents of the alkyl group include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group, a nitro group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxy group, an acyl group, an acyloxy group, an alkyl- or arylsulfonyl group, an acylamino group, and an alkyl- or arylsulfonamido group. Specific examples of the substituted alkyl group are 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl, 2-ethoxycarbonylethyl, 3-methylthiopropyl, 2-acetylaminoethyl, 3-hydroxypropyl, 2-acetyloxyethyl, 3-chloroethyl, 3-methoxyethylallyl, and 4-methyl-2-butenyl groups. R¹ is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
When R¹ is a substituted or unsubstituted aryl group, the aryl group preferably contains 6 to 30 carbon atoms, more preferably 6 to 8 carbon atoms. Examples of the aryl group includes phenyl, naphthyl, 3-sulfophenyl, 4-methoxyphenyl, and 3-lauroylaminophenyl groups.
R¹ is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
When R² in formula (I) is a substituted or unsubstituted alkyl group, the alkyl group preferably contains 1 to 30 carbon atoms, more preferably 8 to 22 carbon atoms. Examples of the alkyl group as R² are the same as those enumerated for R¹.
When R² is a substituted or unsubstituted aryl group, the aryl group preferably contains 6 to 30 carbon atoms. The aryl group is preferably a substituted one. Examples of the aryl group as R² are the same as those listed for R¹.
When R² is a substituted or unsubstituted alkylamino group, the alkylamino group preferably contains 1 to 30 carbon atoms, more preferably 8 to 22 carbon atoms. Examples of the alkylamino group are methylamino, diethylamino, and methyloctadecylamino groups.
When R² is a substituted or unsubstituted arylamino group, the arylamino group preferably contains 6 to 30 carbon atoms, more preferably 8 to 22 carbon atoms. Examples of the arylamino group are phenylamino, p-ethylphenylamino, and 3-tetradecylsulfamoylphenylamino groups.
When R² is a substituted or unsubstituted alkoxy group, the alkoxy group preferably contains 1 to 30 carbon atoms, more preferably 8 to 22 carbon atoms. Examples of the alkoxy group are methoxy, ethoxy, dodecyloxy, and benzyloxy groups.
When R² is a substituted or unsubstituted aryloxy group, the aryloxy group preferably contains 6 to 30 carbon atoms, more preferably 6 to 22 carbon atoms. Examples of the aryloxy group are phenoxy, 4-methoxyphenoxy, 3-acetylaminophenoxy, and 3-methoxycarbonylpropyloxy groups.
When R² is a substituted or unsubstituted heterocyclic group, the heterocyclic group preferably contains 2 to 30 carbon atoms, more preferably 8 to 22 carbon atoms. Examples of the heterocyclic group are 2-pyridyl, 1-imidazolyl, benzothiazol-2-yl, morpholino, and benzoxazol-2-yl groups.
The above-mentioned groups may be the terminal of a pendent group bonded to a polymeric molecule. Examples of the polymeric residual group includes a polyethylene residue, a polyvinyl alcohol residue, a polystyrene residue, a polyacrylic residue, and a copolymer thereof.
R² is preferably a substituted or unsubstituted alkyl group having 8 to 22 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
Examples of the substituent for the above substituents represented by R¹ or R² include an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a carboxyl group, a cyano group, a sulfamoyl group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aminocarbonylamino group, a sulfamoylamino group, an amino group, a heterocyclicoxy group, an alkylthio group, an arylthio group, a heterocyclicthio group, a heterocyclic group, an alkylsulfonyl group and an arylsulfonyl group.
Specific examples of the substituent include an aryl group (which may be further substituted, and preferably has 6 to 30 carbon atoms, such as phenyl, m-acetylaminophenyl and p-methoxyphenyl groups), an alkyl group (which may be further substituted, and preferably has 1 to 30 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, n-octyl and n-dodecyl groups), a cyano group, a carboxyl group, an acyl group (preferably having 1 to 30 carbon atoms, such as acetyl, pivaloyl, benzoyl, furoil and 2-pyridyl groups), a carbamoyl group (preferably having 1 to 30 carbon atoms, such as methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl and n-octylcarbamoyl groups), an alkoxycarbonyl group (which may be further substituted, and preferably has 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl and isopropoxycarbonyl groups), an aryloxycarbonyl group (which may be further substituted, and preferably has 7 to 30 carbon atoms, such as phenoxycarbonyl, p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl and o-methoxyphenoxycarbonyl groups), an acylamino group (an alkylcarbonylamino group preferably having 1 to 30 carbon atoms (which may be further substituted, such as folmylamino, acetylamino, propionylamino and cyanoacetylamino groups), an arylcarbonylamino group preferably having 7 to 30 carbon atoms (which may be further substituted, such as benzoylamino, p-toluilamino, pentafluorobenzoylamino and m-methoxybenzoylamino groups), a heterylcarbonylamino group preferably having 4 to 30 carbon atoms (which may be further substituted, such as 2-pyridylcarbonylamino, 3-pyridylcarbonylamino and furoilamino groups)), an alkoxycarbonylamino group (which may be further substituted, and preferably has 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino and methoxyethoxycarbonylamino groups), an aryloxycarbonylamino group (which may be further substituted, and preferably has 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, and o-chlorophenoxycarbonylamino groups), an aminocarbonylamino group (preferably having 1 to 30 carbon atoms, such as methylaminocarbonylamino, ethylaminocarbonylamino, anilinocarbonylamino and dimethylaminocarbonylamino groups), a sulfamoyl group (preferably having 1 to 30 carbon atoms, such as methylaminosulfonylamino, ethylaminosulfonylamino and anilinosulfonylamino groups), an amino group (which includes an anilino group, and preferably has 0 to 30 carbon atoms, such as amino, methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino and anilino groups), an alkoxy group (which may be further substituted, and preferably has 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy and n-dodecyloxy groups), an aryloxy group (which may be further substituted, and preferably has 6 to 30 carbon atoms, such as phenoxy, m-chlorophenoxy, p-methoxyphenoxy and o-methoxyphenoxy groups), a heteryloxy group (which may be further substituted, and preferably has 3 to 30 carbon atoms, such as tetrahydropyranyloxy, 3-pyridyloxy and 2-(1,3-benzoimidazolyl)oxy groups), an alkylthio group (which may be further substituted, and preferably has 1 to 30 carbon atoms, such as methylthio, ethylthio, n-butylthio and t-butylthio groups), an arylthio group (which may be further substituted, and preferably has 6 to 30 carbon atoms, such as phenylthio), a heterylthio group (which may be further substituted, and preferably has 3 to 30 carbon atoms, such as 2-pyridylthio, 2-(1,3-benzoxazolyl)thio, 1-hexadecyl-1,2,3,4-tetrazolyl-5-thio and 1-(3-N-octadecylcarbamoyl)phenyl-1,2,3,4-tetrazolyl-5-thio groups), a heterocyclic group (which may be further substituted, and preferably has 3 to 30 carbon atoms, such as thiadiazolyl and pyrazolyl groups), an alkenyl group (preferably having 3 to 18 carbon atoms, such as vinyl, allyl and 4-methyl-2-butenyl groups), a sulfamoyl group (preferably having 0 to 36 carbon atoms, such as methylsulfamoyl, dimethylsulfamoyl and dioctylsulfamoyl groups), an alkylsulfonylamino group (preferably having 1 to 18 carbon atoms, such as methanesulfonylamino and n-butanesulfonylamino groups), an arylsulfonylamino group (preferably having 6 to 18 carbon atoms, such as benzenesulfonylamino and p-toluenesulfonylamino groups), an alkylsulfonyl group (preferably 1 to 18 carbon atoms, such as methanesulfonyl, ethanesulfonyl and n-octanesulfonyl groups) and an arylsulfonyl group (preferably having 6 to 18 carbon atoms, such as benzenesulfonyl and p-toluenesulfonyl groups).
While the amount of the compound (I) to be incorporated is not particularly limited, it is preferably in the range of from 1.0 x 10^-4 to 1.0 mole, more preferably 1.0 x 10^-3 to 5.0 x 10^-1 mole, per mole of silver (Ag) present in a light-sensitive silver halide emulsion layer to which it is added; or from 1 x 10^-6 to 3 x 10^-3 mol/m², more preferably 1 x 10^-5 to 1 x 10^-3 mol/m², when added to a light-insensitive layer.
The compound (I) can be added either as dissolved in a water-soluble solvent (e.g., methanol, ethanol or acetone) or as dispersed and emulsified together with couplers, and the like. It may also be added previously to a silver halide emulsion preparation system. Addition as dispersed and emulsified is the most preferred.
The layer to which the compound (I) is incorporated is not particularly limited but is preferably a silver halide emulsion layer. Addition to a red-sensitive emulsion layer and/or a green-sensitive emulsion layer is more preferred.
The compound (I) preferably has a molecular weight of 300 or more, more preferably 350 or more, still more preferably 450 or more.
The compound (I) should be substantially insoluble in water so as not to be diffused through a gelatin layer. The term "substantially insoluble in water" means that solubility in water at 25°C is not more than 5% by weight, preferably not more than 1% by weight.
Some of the starting materials for synthesizing compounds (I) (e.g., acid anhydrides and alcohols) cannot but be available as a mixture of isomers or analogues. Such being the case, it is easier to obtain the compound (I) in the form of a mixture of isomers or analogues. In this case, it is preferable to add the mixture containing the compound (I) as obtained to a silver halide light-sensitive material.
Specific but non-limiting examples of the compound (I) are shown below.
The compounds (I) can easily be synthesized by the processes described in JP-A-3-293666 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-59-198453, and U.S. Patents 4,330,606 and 4,339,515.
The image information obtained after development processing of the silver halide color photographic material of the present invention is preferably used by irradiating light to the developed photographic material to thereby read the image information optically, and converting the image information to an electric signal. The electric signal could be used in various ways depending on desired purposes. For example, the electric signal may be provided as a print by a printer, may be displayed on a TV screen to view the image, or may be inputted into a computer to be processed. The phrase "irradiating light to the developed photographic material to thereby read the image information optically" means to read the image information corresponding to an entire image screen by scanning a part of the screen with irradiated light. An example of this step is to read information with a CCD line sensor.
The light-sensitive material according to the present invention comprises a support having thereon at least one light-sensitive layer. A typical example is a silver halide photographic material comprising a support having thereon at least one color-sensitive layer unit composed of a plurality of silver halide emulsion layers which have substantially the same color sensitivity (sensitivity to blue light, green light or red light) but differ in sensitivity. In a multilayer silver halide color photographic material, such light-sensitive layer units are generally provided on a support in the order of a red-sensitive layer unit, a green-sensitive layer unit, and a blue-sensitive layer unit from the support side. Depending on the purpose, the order of the layer units may be reversed, and a color-sensitive layer unit may have therein a light-sensitive layer of different color sensitivity. A light-insensitive layer may be provided as an intermediate layer between the above-described silver halide light-sensitive layers, or as a bottom layer or a top layer. The light-insensitive layers may contain couplers, DIR compounds, color mixing preventives, etc. as hereinafter described.
Each light-sensitive layer unit generally has a two-layer structure composed of a high-speed emulsion layer and a low-speed emulsion layer as described in West German Patent 1,121,470 and British Patent 923,045, which are preferably provided with the sensitivity descending toward the support. It is also possible to provide a low-speed emulsion layer on the side farther from the support, and a high-speed emulsion layer on the side closer to the support, as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541, and JP-A-62-206543.
Examples of layer orders include an order of low-speed blue-sensitive layer (BL)/high-speed blue-sensitive layer (BH)/high-speed green-sensitive layer (GH)/low-speed green-sensitive layer (GL)/high-speed red-sensitive layer (RH)/low-speed red-sensitive layer (RL), an order of BH/BL/GL/GH/RH/RL, and an order of BH/BL/GH/GL/RL/RH, each from the side farthest from the support.
The light-sensitive layers may be arranged in the order of blue-sensitive layer/GH/RH/GL/RL from the side farthest from the support as described in JP-B-55-34932 (the term "JP-B" as used herein means an "examined published Japanese patent application"), or in the order of blue-sensitive layer/GL/RL/GH/RH from the side farthest from the support as described in JP-A-56-25738 and JP-A-62-63936.
A light-sensitive layer unit may be composed of three layers whose sensitivity varies in a descending order toward the support, i.e., the highest-speed emulsion layer as the upper layer, a middle-speed emulsion layer as an intermediate layer, and the lowest-speed emulsion layer as the lower layer, as proposed in JP-B-49-15495. Three layers of different sensitivity in each layer unit may also be arranged in the order of middle-speed emulsion layer/high-speed emulsion layer/low-speed emulsion layer from the side farther from a support as described in JP-A-59-202464.
Furthermore, an order of high-speed emulsion layer/low-speed emulsion layer/middle-speed emulsion layer or an order of low-speed emulsion layer/middle-speed emulsion layer/high-speed emulsion layer are also employable. In the case where a layer unit is composed of 4 or more layers, the order of layers may be altered similarly.
An interlayer effect-donating layer (CL) which has a different spectral sensitivity distribution from that of a main light-sensitive layer (BL, GL or RL) is preferably provided next or close to the main light-sensitive layer for the purpose of improving color reproducibility, as described in U.S. Patents 4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448, and JP-A-63-89850.
The silver halide used in the present invention preferably includes silver iodobromide, silver iodochloride, and silver iodochlorobromide, each containing not more than about 30 mol% of silver iodide. Silver iodobromide or silver iodochlorobromide containing about 2 to about 10 mol% of silver iodide are particularly preferred.
The silver halide grains in the photographic emulsions include those having a regular crystal form, such as a cubic form, an octahedral form or a tetradecahedral form, those having an irregular crystal form, such as a spherical form or a plate form, those having a crystal defect, such as a twin plane, and those having a complex form of these crystal forms.
The silver halide grains may have a broad range of size, may be about 0.2 µm in particle diameter or even smaller up to about 10 µm in terms of projected area diameter. The emulsion may be either a polydispersed emulsion or a monodispersed emulsion.
The silver halide emulsions to be used in the present invention can be prepared by known techniques described, e.g., in Research Disclosure, No. 17643, pp. 22-23, "I. Emulsion preparation and types" (Dec., 1978), ibid., No. 18716, p. 648 (Nov., 1979), ibid., No. 307105, pp. 863-865 (Nov., 1989), P. Glafkides, Chemie et Phisique Photographique, Paul Montel (1967), G.F. Duffin, Photographic Emulsion Chemistry, Focal Press (1966), and V.L. Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press (1964).
The monodispersed emulsions described in U.S. Patents 3,574,628 and 3,655,394 and British Patent 1,413,748 are preferably used.
Tabular grains having an aspect ratio of about 3 or more are also useful in the present invention. The tabular grains can easily be prepared by known processes described, e.g., in Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4.433,048, and 4,439,520, and British Patent 2,112,157.
The silver halide grains may have a homogeneous crystal structure, or may have a heterogeneous structure in which the inside and the outside have different halogen compositions, or may have a layered structure. Silver halides of different composition may be fused by epitaxy. Compounds other than silver halides, such as silver thiocyanate or lead oxide, may be fused to silver halide grains. Furthermore, a mixture of various grains having different crystal forms may be used.
The emulsions may be any of a surface latent image type which forms a latent image predominantly on the surface of the grains, an internal latent image type which forms a latent image predominantly in the inside of the grains, and a type which forms a latent image both on the surface and in the inside. Anyway, the emulsion must be of negative type. The internal latent image type emulsion may be a core/shell type emulsion as described in JP-A-63-264740. The process for preparing a core/shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness is preferably 3 to 40 nm, more preferably 5 to 20 nm, while varying depending on development processing, etc.
The silver halide emulsions are usually used after being subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in these steps are described in Research Disclosure, Nos. 17643, 18716, and 307105 as hereinafter tabulated.
A mixture of two or more emulsions different in at least one characteristics of grain size, grain size distribution, halogen composition, grain shape, and sensitivity may be used in the same layer.
Surface fogged silver halide grains described in U.S. Patent 4,082,553, internal fogged silver halide grains described in U.S. Patent 4,626,498 and JP-A-59-214852, and colloidal silver are preferably applied to light-sensitive silver halide emulsion layers and/or substantially light-insensitive hydrophilic colloid layers. The terminology "surface or internal fogged silver halide grains" as used herein means silver halide grains which are developable uniformly (i.e., non-imagewise) irrespective of exposure. The method for preparing these fogged grains is described in U.S. Patent 4,626,498 and JP-A-59-214852. In internal fogged core/shell type grains, the silver halide forming the core may have a different halogen composition. Internal or surface fogged silver halides may be any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. The fogged grains preferably have an average grain size of 0.01 to 0.75 µm, particularly preferably 0.05 to 0.6 µm. The fogged grains may be regular crystals and may be either polydispersed or monodispersed but are preferably monodispersed (at least 95% by weight or number of the total grains have a grain size falling within ±40% of an average grain size).
It is preferable to use light-insensitive fine silver halide grains in the present invention. The terminology "light-insensitive fine silver halide grains" as used herein means fine silver halide grains which are insensitive to imagewise exposure for color image formation and therefore undergo substantially no development in the subsequent development processing. It is preferable for the light-insensitive fine silver halide grains not to be fogged previously. The fine silver halide grains have a silver bromide content of from 0 up to 100 mol% and, if necessary, may contain silver chloride and/or silver iodide, preferably contain 0.5 to 10 mol% of silver iodide. The fine silver halide grains preferably have an average grain size (an average projected area circle-equivalent diameter) of 0.01 to 0.5 µm, more preferably 0.02 to 0.2 µm.
The fine silver halide grains can be prepared in the same manner as for general light-sensitive silver halide grains. The surface of the fine silver halide grains needs neither optical sensitization nor spectral sensitization. It is preferable to add known stabilizers, such as triazoles, azaindenes, benzothiazolium salts, mercapto compounds, and zinc compounds, to the fine silver halide grains prior to addition to a coating composition. Colloidal silver may be incorporated into the layer containing the fine silver halide grains.
The light-sensitive materials according to the present invention preferably have a coated amount of silver of not more than 6.0 g/m², more preferably not more than 4.5 g/m².
Known photographic additives which can be used in the present invention are described in Research Disclosure, Nos. 17643, 18716, and 307105 as tabulated below.
While various color forming couplers can be used in the light-sensitive materials of the present invention, the following couplers are particularly preferred.

Yellow Couplers:

Couplers represented by formulae (I) and (II) of EP 502,424A, couplers represented by formulae (1) and (2) of EP 513,496A (especially Y-28 on page 18), couplers represented by formula (I) claimed in claim 1 of EP 568,037A, couplers represented by formula (I) of U.S. Patent 5,066,576, col. 1, lines 45-55, couplers represented by formula (I) of JP-A-4-274425, couplers claimed in claim 1 (page 40) of EP 498,381A1 (especially D-35 on page 18), couplers represented by formula (Y) of EP 447,969A1, page 4 (especially Y-1 on page 17 and Y-54 on page 41), and couplers represented by formulae (II) to (IV) of U.S. Patent 4,476,219, col. 7, lines 36-58 (especially II-17 and 19 in col. 17 and II-24 in col. 19).

Magenta Coupler:

Couplers of JP-A-3-39737 (L-57 in the lower right part of page 11, L-68 in the lower right part of page 12, and L-77 in the lower right part of page 13; couplers of EP 456,257 ([A-4]-63 on page 134 and [A-4]-73 and -75 on page 139); couplers of EP 486,965 (M-4 and -6 on page 26 and M-7 on page 27); couplers of EP 571,959A (M-45 on page 19); couplers of JP-A-5-204106 (M-1 on page 6); and couplers of JP-A-4-362631 (M-22).

Cyan Coupler:

Couplers of JP-A-4-204843 (CX-1, 3, 4, 5, 11, 12, 14, and 15 on pp. 14-16; couplers of JP-A-4-43345 (C-7 and 10 on p. 35, C-34 and 35 on p. 37, and (I-1) and (I-17) on pp. 42-43); and couplers represented by formulae (Ia) or (Ib) claimed in claim 1 of JP-A-6-67385.

Polymer Coupler:

P-1 and P-5 (p. 11) of JP-A-2-44345.
Examples of suitable couplers which develop a dye having moderate diffusibility are described in U.S. Patent 4,366,237, British Patent 2,125,570, EP 96,873B, and West German Patent (OLS) No. 3,234,533.
Examples of suitable colored couplers which can be used for correcting unnecessary absorption of a developed dye are yellow-colored cyan couplers represented by formulae (CI), (CII), (CIII), and (CIV) described in EP 456,257A1, page 5 (especially YC-86 on page 84); yellow-colored magenta couplers ExM-7 (page 202), EX-1 (page 249), and EX-7 (page 251) of EP 456,257A1; magenta-colored cyan couplers CC-9 (col. 8) and CC-13 (col. 10) of U.S. Patent 4,833,069; coupler (2) (col. 8) of U.S. Patent 4,837,136; and colorless masking couplers represented by formula (A) claimed in claim 1 of WO 92/11575 (especially the compounds exemplified on pp. 36-45).
Compounds (inclusive of couplers) capable of releasing a photographically useful residue on reacting with an oxidized developing agent include development inhibitor-releasing compounds, such as the compounds represented by formulae (I) to (IV) on page 11 of EP 378,236A1 (especially T-101 on p. 30, T-104 on p. 31, T-113 on p. 36, T-131 on p. 45, T-144 on p. 51, and T-158 on p. 58), the compounds represented by formula (I) on page 7 of EP 436,938A2 (especially D-49 on p. 51), the compounds represented by formula (1) of EP 568,037A (especially (23) on p. 11), and the compounds represented by formulae (I) to (III) on pages 5 to 6 of EP 440,195A2 (especially I-(1) on p. 29); bleaching accelerator-releasing compounds, such as the compounds represented by formulae (I) and (I') on page 5 of EP 310,125A2 (especially (60) and (61) on p. 61) and the compounds represented by formula (I) claimed in claim 1 of JP-A-6-59411 (especially (7) on p. 7); ligand-releasing compounds, such as the compounds represented by formula LIG-X claimed in claim 1 of U.S. Patent 4,555,478 (especially the compounds in col. 12, lines 21-41); leuco dye-releasing compounds, such as compounds 1 to 6 in cols. 3 to 8 of U.S. Patent 4,749,641; fluorescent dye-releasing compounds, such as the compounds represented by formula COUP-DYE claimed in claim 1 of U.S. Patent 4,774,181 (especially compounds 1 to 11 in cols. 7 to 10); development accelerator- or fogging agent-releasing compounds, such as the compounds represented by formulae (1) to (3) in col. 3 of U.S. Patent 4,656,123 (especially (I-22) in col. 25), and ExZK-2 on p. 75, 11. 36 to 38 of EP 450,637A2; and compounds releasing a group which becomes a dye on release, such as the compounds represented by formula (I) claimed in claim 1 of U.S. Patent 4,857,447 (especially Y-1 to Y-19 in cols. 25-36).
Additives other than couplers which can preferably be used in the present invention are as follows. Dispersing media for oil-soluble organic compounds include P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, and 93 of JP-A-62-215272 (pp. 140-144). Impregnating latices of oil-soluble organic compounds include those described in U.S. Patent 4,199,363. Scavengers for an oxidized developing agent include the compounds represented by formula (I) of U.S. Patent 4,978,606, col. 2, 11. 54-62 (especially I-(1), (2), (6) and (12) in cols. 4-5) and the compounds in col. 2, 11. 5-10 of U.S. Patent 4,923,787 (especially compound 1 in col. 3). Stain inhibitors include the compounds of formulae (I) to (III) on p. 4, 11. 30-33 of EP 298321A (especially I-47, I-72, III-1 and III-27 on pp. 24-48). Discoloration inhibitors include A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, and 164 on pp. 69-118 of EP 298321A1; II-1 to III-23 in cols. 25-38 of U.S. Patent 5,122,444 (especially III-10); I-1 to III-4 on pp. 8-12 of EP 471347A (especially II-2); and A-1 to 48 in cols. 32-40 of U.S. Patent 5,139,931 (especially A-39 and 42). Materials for reducing the amount of color formation enhancing agents or color amalgamation inhibitors include I-1 to II-15 on pp. 5-24 of EP 411324A (especially I-46). Formalin scavengers include SCV-1 to 28 on pp. 24-29 of EP 477932A (especially SCV-8). Hardening agents include H-1, 4, 6, 8 and 14 on p. 17 of JP-A-1-214845, the compounds represented by formulae (VII) to (XII) in cols. 13-23 of U.S. Patent 4,618,573 (H-1 to 54), the compounds represented by formula (6) in the right lower part on page 8 of JP-A-2-214852 (H-1 to 76, especially H-14), and the compounds claimed in claim 1 of U.S. Patent 3,325,287. Development inhibitor precursors include P-24, 37 and 39 on pp. 6-7 of JP-A-62-168139, and the compounds claimed in claim 1 of U.S. Patent 5,019,492 (especially 28 and 29 in col. 7). Antiseptics and antifungal agents include I-1 to III-43 in cols. 3-15 of U.S. Patent 4,923,790 (especially II-1, 9, 10 and 18 and III-25). Stabilizers and antifoggants include I-1 to (14) in cols. 6-16 of U.S. Patent 4,923,793 (especially I-1, 60, (2) and (13)), and compounds 1 to 65, especially 36, in cols. 25-32 of U.S. Patent 4,952,483. Chemical sensitizers include triphenylphosphine selenide, and compound 50 of JP-A-5-40324. Dyes include a-1 to b-20 (especially a-1, 12, 18, 27, 35 and 36 and b-5) on pp. 15-18 of JP-A-3-156450 and V-1 to 23 (especially V-1) on pp. 27-29, F-I-1 to F-II-43 (especially F-I-11 and F-II-8) on pp. 33-55 of EP 445627A, III-1 to 36 (especially III-1 and 3) on pp. 17-28 of EP 457153A, microcrystalline dispersions of Dye-1 to 124 on pp. 8-26 of WO 88/04794, compounds 1 to 22 on pp. 6-11 of EP 319999A (especially compound 1), compounds D-1 to 87 (pp. 3-28) represented by formulae (1) to (3) of EP 519306A, compounds 1 to 22 (cols. 3-10) represented by formula (I) of U.S. Patent 4,268,622, and compounds (1) to (31) (cols. 2 to 9) represented by formula (I) of U.S. Patent 4,923,788. Ultraviolet absorbers include compounds (18b) to (18r) and 101 to 427 (pp. 6-9) represented by formula (1) of JP-A-46-3335, compounds (3) to (66) (pp. 10-44) represented by formula (I) and compounds HBT-1 to 10 (p. 14) represented by formula (III) of EP 520938A, and compounds (1) to (31) (cols. 2-9) represented by formula (1) of EP 521823A.
The present invention is applicable to a variety of color light-sensitive materials, such as color negative films for general use or for motion pictures, color reversal films for slides or TV, color paper, color positive films, and color reversal paper. The present invention is also suited to film units with a lens described in JP-B-2-32615 and JP-B-U-3-39784 (the term "JP-B-U" as used herein means an "examined published Japanese utility model application").
In the light-sensitive materials of the present invention, the hydrophilic colloidal layers on the side having emulsion layers preferably have a total film thickness of not more than 28 µm, more preferably not more than 23 µm, still more preferably not more than 18 µm, and particularly preferably not more than 16 µm, and a rate of swelling T_1/2 of not more than 30 seconds, more preferably not more than 20 seconds. The terminology "film thickness" as used herein means a film thickness as measured after conditioning at 25°C and a relative humidity of 55% for 2 days. The terminology "rate of swelling T_1/2" means a time required for a light-sensitive material to be swollen to 1/2 the saturated swollen thickness, the saturated swollen thickness being defined to be 90% of the maximum swollen thickness which is reached when the light-sensitive material is swollen with a color developer at 30°C for 3 minutes and 15 seconds. The rate of swelling can be measured with a swellometer of the type described in A. Green, et al., Photographic Science and Engineering, Vol. 19, No. 2, pp. 124-129.
T_1/2 can be controlled by adding a proper amount of a hardening agent for a gelatin binder or by varying aging conditions after coating.
Furthermore, the light-sensitive material preferably has a degree of swelling of from 150 to 400%. The terminology "degree of swelling" as used herein means a value obtained from the maximum swollen film thickness as defined above according to formula: (maximum swollen film thickness - film thickness)/film thickness.
The light-sensitive material of the present invention preferably has a hydrophilic colloidal layer(s) called a backing layer having a total dry thickness of from 2 to 20 µm on the side opposite to the emulsion layer side. The backing layer preferably contains the above-described additives, e.g., light absorbers, filter dyes, ultraviolet absorbers, antistatic agents, hardening agents, binders, plasticizers, lubricants, coating aids, and surface active agents. The backing layer preferably has a degree of swelling of from 150 to 500%.
The photographic materials can be development processed in a conventional manner as described in Research Disclosure, No. 17643, pp. 28-29, ibid., No. 18716, p. 651, left to right columns, and ibid., No. 307105, pp. 880-881.
Processing solutions used for processing color negative films according to the present invention are described below.
The compounds described in JP-A-4-121739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used as color developing agent of a color developer used in the present invention. Color developing agents which are particularly preferred for rapid processing include 2-methyl-4-[N-ethyl-N-(2-hydroxyethyl)amino]aniline, 2-methyl-4-[N-ethyl-N-(3-hydroxypropyl)amino]aniline, and 2-methyl-4-[N-ethyl-N-(4-hydroxybutyl)amino]aniline.
The color developing agent is preferably used in a color developer in a concentration of 0.01 to 0.08 mol per liter of the color developer, more preferably 0.015 to 0.06 mol/l, particularly preferably 0.02 to 0.05 mol/l. A color developer replenisher preferably contains the color developing agent at 1.1 to 3 times, particularly 1.3 to 2.5 times, the concentration in the color developer.
Hydroxylamine is broadly used as preservative of the color developer. Where higher preservability is demanded, hydroxylamine derivatives having such substituents as an alkyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group are preferred. Such hydroxylamine derivatives include N,N-di(sulfoethyl)hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, and N,N-di(carboxyethyl)hydroxylamine. di(carboxyethyl)hydroxylamine. Among these, is particularly preferred. While these hydroxylamine derivatives may be used in combination with hydroxylamine, it is preferable to use one or more thereof in place of hydroxylamine.
The preservative is preferably used in a concentration of 0.02 to 0.2 mol/l, more preferably 0.03 to 0.15 mol/l, particularly preferably 0.04 to 0.1 mol/l. Similarly to the color developing agent, the preservative is added to the replenisher in 1.1 to 3 times the concentration of the tank solution.
The color developer contains a sulfite as a preservative for preventing the oxidation product of the color developing agent from getting tar-like. A sulfite preservative is preferably used in a concentration of 0.01 to 0.05 mol/l, more preferably 0.02 to 0.04 mol/l. It is added to the replenisher in 1.1 to 3 times the concentration of the tank solution.
The color developing solution is adjusted preferably to a pH of 9.8 to 11.0, more preferably 10.0 to 10.5. The pH of the replenisher is preferably 0.1 to 1.0 higher than that of the tank solution. In order to maintain the pH at a prescribed value stably, known buffering agents, such as carbonates, phosphates, sulfosalicylates, and borates, are used.
The rate of replenishment of the color development tank with a color developer replenisher is preferably 80 to 1300 ml per m² of a processed light-sensitive material. From the standpoint of pollution loading reduction, it is more preferred to further reduce the rate of replenishment to, e.g., 80 to 600 ml/m², particularly 80 to 400 ml/m².
The color developer usually has a bromide ion concentration of 0.01 to 0.06 mol/l. For the purpose of suppressing fog while retaining the sensitivity thereby to improve discrimination and also improving graininess, a preferred bromide ion concentration is 0.015 to 0.03 mol/l. The above bromide ion concentration of the color developer can be maintained by adding bromide ions to the replenisher in a concentration (C) calculated according to the following formula. When C is negative, it is preferable to add no bromide ion to the replenisher. C = A - W/V wherein C represents a bromide ion concentration (mol/l) in a replenisher; A represents a target bromide ion concentration (mol/l) of a color developer (tank solution); W represents the amount of bromide ions (mol) dissolved out of 1 m² of a light-sensitive material during color development processing; and V represents the amount of the replenisher (ℓ) per m² of a light-sensitive material processed.
In a color development system using a reduced rate of replenishment or a high bromide ion concentration, it is preferable for increasing the sensitivity to add a development accelerator, such as pyrazolidone compounds (e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone) and thioether compounds (e.g., 3,6-dithia-1,8-octanediol).
For bleaching, 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 adopted.
Bleaching agents which provide a redox potential of not lower than 150 mV, for example those described in JP-A-5-72694 and JP-A-5-173312 are preferred. Among them 1,3-diaminopropanetetraacetic acid and the compound No. 1 described in JP-A-5-173312, page 7 (an iron (III) complex) are particularly preferred.
In order to improve biodegradability of the processing solution, it is preferable to use the iron (III) complexes described in JP-A-4-251845, JP-A-4-268552, EP 588,289, EP 591,934, and JP-A-6-208213 as a bleaching agent. These bleaching agents are preferably used at a concentration of 0.05 to 0.3 mol per liter of the processing solution having bleaching ability. In particular, a concentration of 0.1 to 0.15 mol/l is preferred for reduction of the output into the environment. A bleaching solution as processing solution having bleaching ability preferably contains 0.2 to 1 mol/l, particularly 0.3 to 0.8 mol/l, of bromides.
The replenisher of the processing solution having bleaching ability contains components in concentrations (C_R) calculated according to the following formula, whereby the concentrations in the tank solution can be maintained constant. CR = CT x (V1 + V2)/V1 + CP wherein C_R represents the concentration of a component in a replenisher; C_T represents the concentration of the component in a tank solution; C_P represents the concentration of the component consumed during processing; V₁ represents the amount of the replenisher (ml) per m² of a light-sensitive material processed; and V₂ represents the amount of a carry-over (ml) from the prebath per m² of a light-sensitive material.
The bleaching solution preferably contains a pH buffering agent. Dicarboxylic acids giving off less odor, such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid, are preferred pH buffering agents. Known bleaching accelerators described, e.g., in JP-A-53-95630, Research Disclosure, No. 17129, and U.S. Patent 3,893,858, are preferably used.
The bleaching bath is preferably replenished with a bleaching replenisher at a rate of 50 to 1000 ml, more preferably 80 to 500 ml, particularly preferably 100 to 300 ml, per m² of a light-sensitive material. The bleaching solution is preferably aerated.
For fixing, the compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be adopted.
In order to improve the rate of fixation and preservability of the processing solution it is preferable to add to the processing solution having fixing ability the compound represented by formula (I) and the compound represented by formula (II) of JP-A-6-301169 either individually or as a combination thereof. It is also preferable for improvement of preservability to use a p-toluenesulfinate or the sulfinic acid compound described in JP-A-1-224762.
While it is preferable for improvement of desilvering performance to use ammonium as cation in the processing solution having bleaching ability or fixing ability, it is preferred to use no ammonium or at least to reduce its amount from the viewpoint of reducing environmental pollution.
It is particularly preferable to apply a jet agitation system to the bleaching, blix and fixing steps as described in JP-A-1-309059.
The rate of replenishment in the blix or fixing step is preferably 100 to 1000 ml, more preferably 150 to 700 ml, particularly preferably 200 to 600 ml, per m² of a light-sensitive material.
A means for silver recovery is preferably placed in-line or off-line in the blix or fixing step to recover silver. An in-line means for silver recovery enables reduction of silver concentration in the processing solution thereby to reduce the rate of replenishment. It is also preferable to reuse the residual processing solution separated in the off-line means for silver recovery as a replenisher.
The blix or fixing step may be carried out in a plurality of processing tanks, which are connected by cascade piping to form a multistage countercurrent system. In view of the size balance with a developing machine, a two-tank cascade system is generally efficient, with the processing time ratio of the preceding tank to the following tank preferably ranging form 0.5:1 to 1:0.5, more preferably from 0.8:1 to 1:0.8.
For improved preservability, a free chelating agent is preferably added to the blix solution or fixing solution. The biodegradable chelating agents hereinabove mentioned as to the bleaching solution are preferred.
For washing and stabilization, the disclosure of JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16 can be preferably adopted. It is particularly preferred for conservation of the working environment to use azolylmethylamines described in EP 504,609 and EP 519,190 or N-methylolazoles described in JP-A-4-362943 in the stabilizing solution in place of formaldehyde or to use dimerized magenta couplers and to use a stabilizing solution comprising surfactants and containing no image stabilizers such as formaldehyde.
The stabilizing solution described in JP-A-6-289559 is preferably used for reducing adhesion of dust onto a magnetic recording layer provided on a light-sensitive material.
In order to ensure the washing or stabilizing function and to reduce the waste solution output for environmental conservation, the rate of replenishment in washing and stabilizing steps is preferably 80 to 1000 ml, still preferably 100 to 500 ml, particularly preferably 150 to 300 ml, per m² of a light-sensitive material. In processing with such low-throughput replenishment, it is preferable to prevent growth of bacteria and mold by adding known antifungal agents (e.g., thiabendazole, 1,2-benzoisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one) or antibiotics (e.g., gentamicin) or subjecting processing water to deionizing with ion-exchange resins, etc. A combined use of deionized water and an antifungal agent or antibiotic is more effective.
It is also preferable that the processing solution in the washing tank or stabilization tank is subjected to treatment with a reverse osmosis membrane as described in JP-A-3-46652, JP-A-3-53246, JP-A-3-55542, JP-A-3-121448, and JP-A-3-126030 thereby to reduce the rate of replenishment. The reverse osmosis membrane to be used is preferably a low-pressure reverse osmosis membrane.
In the present invention it is especially preferred to carry out corrections for evaporation loss of processing solutions according to Technical Disclosure Bulletin 94/4992 (published by Japan Institute of Invention and Innovation). In particular, corrections are preferably made by utilizing the temperature and humidity information of the environment surrounding a developing machine in accordance with Formula 1 on page 2 of the bulletin. Water used for evaporation corrections is preferably taken from the replenisher tank of washing. In this case, deionized water is preferably used as water of a washing replenisher.
Processing chemicals to be used in the present invention are preferably those described in the above bulletin, page 3, right column, line 15 to page 4, left column, line 32. The film processor described in ibid, page 3, right column, lines 22 to 28 is preferably used as a developing machine to be used therefor.
Specific examples of processing chemicals, automatic developing machines, and evaporation correction systems which are preferred in carrying out the present invention are described in ibid, page 5, right column, line 11 to page 7, right column, the last line.
The processing chemicals can be supplied in any form, such as prepared solutions having a concentration of use (working solutions) or as concentrated, granules, powders, tablets, pastes, and emulsions. Available forms include solutions put in a low oxygen-permeable container disclosed in JP-A-63-17453, vacuum packaged powder or granules disclosed in JP-A-4-19655 and JP-A-4-230748, granules containing a water-soluble polymer disclosed in JP-A-4-221951, tablets disclosed in JP-A-51-61837 and JP-A-6-102628, and pastes disclosed in unexamined published Japanese patent application No. Sho. 57-500485 which is based on a PCT application. While any of these forms can be used, working solutions are preferred for convenience on use.
Containers for putting these chemicals in are made of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, etc., either singly or as a composite material thereof. The material of a container is selected in agreement with the demanded level of oxygen permeability. For example, low oxygen-permeable materials, such as polyethylene terephthalate or a composite material of polyethylene and nylon, are preferred for solutions susceptible to oxidation, such as a color developer. The containers preferably have a wall thickness of 500 to 1500 µm and an oxygen permeability of not more than 20 ml/m²·24 hrs·atm.
Processing solutions used for processing the color reversal films according to the invention are described below.
Processing of color reversal films is described in detail in Kochi Gijutsu, No. 6 (Apr., 1, 1991), p. 1, 1. 5 to p. 10, 1. 5 and p. 15, 1. 8 to p. 24, l. 2 (published by Aztec Co., Ltd.) All the techniques disclosed therein can be applied preferably.
In processing of color reversal films, an image stabilizer is added to either a conditioning bath or a final bath. Image stabilizers used include formalin, formaldehyde-sodium bisulfite, and N-methylolazoles. From the standpoint of the working environment, formaldehyde-sodium bisulfite or N-methylolazoles are preferred. The N-methylolazoles preferably include N-methyloltriazole. The particulars previously mentioned as to the color developer, bleaching solution, fixing solution, washing water used for processing of color negative films are also useful for processing of color reversal films.
Preferred processing chemicals for color reversal films, which satisfy the above-mentioned conditions, include E-6 produced by Eastman Kodak Co. and CR-56 produced by Fuji Photo Film Co., Ltd.
The magnetic recording layer used in the present invention will be described below.
The magnetic recording layer used in the present invention is a layer formed by coating a support with an aqueous or organic solvent coating composition comprising a binder having dispersed therein magnetic particles.
The magnetic particles which can be used in the present invention include ferromagnetic iron oxides, e.g., γ-Fe₂O₃, Co-coated γ-Fe₂O₃, Co-coated magnetite, Co-doped magnetite, ferromagnetic chromium dioxide, ferromagnetic metals, ferromagnetic alloys, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, and Ca ferrite. Co-coated ferromagnetic iron oxides, e.g., Co-coated γ-Fe₂O₃, are preferred. The magnetic particles may have an acicular form, a grain form, a spherical form, a cubic form, a plate form and other ones. The magnetic particles preferably have a specific surface area of 20 m²/g or more, more preferably 30 m²/g or more, in terms of BET specific surface area. The ferromagnetic particles preferably have a saturation magnetization (σs) of 3.0 x 10⁴ to 3.0 x 10⁵ A/m, particularly 4.0 x 10⁴ to 2.5 x 10⁵ A/m. The ferromagnetic particles may be surface-treated with silica and/or alumina or an organic substance. The ferromagnetic particles may further be surface-treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. The magnetic particles coated with an organic or inorganic substance described in JP-A-4-259911 and JP-A-5-81652 are also useful.
The binders used for the magnetic particles include thermoplastic resins, thermosetting resins, radiation-curing resins, reactive resins, acid-, alkali- or biodegradable polymers, naturally occurring polymers (e.g., cellulose derivatives and sugar derivatives), and mixtures thereof, as described in JP-A-4-219569. These binder resins have a glass transition temperature (hereinafter abbreviated as Tg) of -40°C to 300°C and a weight average molecular weight of 2,000 to 1,000,000. Examples of useful binder resins are vinyl copolymers, cellulose derivatives, such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins. Gelatin is also preferred. Cellulose di(or tri)acetate is particularly preferred. The binder can be made curable by addition of an epoxy, aziridine or isocyanate crosslinking agent. Examples of the isocyanate crosslinking agent include isocyanates, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate; reaction products between these isocyanates and polyhydric alcohols (e.g., a reaction product between 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane); and polyisocyanates obtained by condensation of these isocyanates. These isocyanate crosslinking agents are described, e.g., in JP-A-6-59357.
Preferred means for dispersing magnetic particles in the binder include a kneader, a pin mill, an annular mill, and a combination thereof as described in JP-A-6-35092. The dispersants described in JP-A-5-88283 and other known dispersants can be used. The magnetic recording layer usually has a thickness of 0.1 to 10 µm, preferably 0.2 to 5 µm, more preferably 0.3 to 3 µm. A magnetic particles to binder weight ratio is preferably 0.5:100 to 60:100, more preferably 1:100 to 30:100. The magnetic particles are usually applied in a coated amount of 0.005 to 3 g/m², preferably 0.01 to 2 g/m², more preferably 0.02 to 0.5 g/m². The magnetic recording layer preferably has a transmission yellow density of 0.01 to 0.50, more preferably 0.03 to 0.20, particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the back side of a support by coating or printing either over the entire surface or in a stripe or stripes. Useful coating techniques include air doctor coating, blade coating, air knife coating, squeegee coating, impregnation, reverse roll coating, transfer roll coating, gravure coating, kiss roll coating, casting, spraying, dip coating, bar coating, and extrusion coating. The coating composition described in JP-A-5-341436 is preferred.
The magnetic recording layer can have other functions such as lubricity improvement, curl control, static electricity prevention, blocking prevention, and head polishing. These functions may be performed by separately provided functional layers. Abrasives comprising non-spherical inorganic grains at least one kind of which has a Mohs hardness of 5 or higher are preferably used. Such non-spherical inorganic grains preferably include fine particles of oxides, such as aluminum oxide, chromium oxide, silicon dioxide, and titanium dioxide; carbides, such as silicon carbide and titanium carbide; and diamond. These abrasives can be surface-treated with a silane coupling agent or a titanium coupling agent. The grains may be incorporated into the magnetic recording layer or be applied over the magnetic recording layer as a protective layer or a lubricating layer, etc. In the latter case, the above-enumerated binders can be used. The same binder as used in the magnetic recording layer is preferred. The particulars of light-sensitive materials having a magnetic recording layer are disclosed in U.S. Patents 5,336,589, 5,250,404, 5,229,259, and 5,215,874, and EP 466,130.
Examples of supports which can be suitably used in the light-sensitive materials of the present invention are described, e.g., in Research Disclosure, No. 17643, p. 28, ibid., No. 18716, p. 647, right column to p. 648, left column, and ibid., No. 307105, p. 879.
A polyester support which is preferably used in the present invention is roughly described below. For the details of the support as well as the light-sensitive materials, processing procedures, cartridges, and working examples therefor, reference can be made to Technical Disclosure Bulletin 94/6023 (published on Mar. 15, 1994 by Japan Institute of Invention and Innovation). The polyester used in the present invention is obtainable essentially from a diol and an aromatic dicarboxylic acid. The aromatic dicarboxylic acid includes 2,6-, 1,5-, 1,4- or 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, and phthalic acid. The diol includes diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenols such as bisphenol A. Specific examples of the polyesters include homopolymers, such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Polyesters comprising 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid unit are preferred. Polyethylene 2,6-naphthalate is particularly preferred. These polyesters have an weight-average molecular weight of about 5,000 to 200,000. The polyesters for use in the present invention have a Tg of not lower than 50°C, preferably not lower than 90°C.
In order to reduce liability to curling, it is preferable that a polyester film is subjected to a heat treatment at a temperature of 40°C and below the Tg, more preferably at or above (Tg - 20°C) and below the Tg. The heat treatment can be carried out at a constant temperature or while cooling within the above temperature range. The heat treatment time is from 0.1 to 1500 hours, preferably 0.5 to 200 hours. The polyester film can be heat-treated in a roll form or while moved in a web form. The surface properties of the support can be improved by providing surface unevenness, for example, by applying conductive inorganic particles, e.g., SnO₂ or Sb₂O₅. It is preferable to knurl one end of the support to slightly increase the thickness so as to prevent the cut edge from leaving a mark at the core of a roll film. The heat treatment may be performed at any stage after support film formation, after surface treatment, after formation of a backing layer (application of an antistatic agent, a lubricant, etc.), or after formation of a subbing layer. It is preferably conducted after application of an antistatic agent.
The polyester may contain an ultraviolet absorber. Furthermore, light piping can be prevented by incorporating into the polyester a dye or a pigment commercially available for polyesters, such as "Diaresin" produced by Mitsubishi Chemical Industries Ltd. and "Kayaset" produced by Nippon Kayaku Co., Ltd.
In order to improve adhesion of the support and layers constituting a light-sensitive material, the support is preferably subjected to surface activating treatment, such as a chemical treatment, a mechanical treatment, a corona discharge treatment, a flame treatment, an ultraviolet treatment, a high frequency treatment, a glow discharge treatment, an active plasma treatment, a laser treatment, a mixed acid treatment, and an ozone oxidation treatment. Preferred of these surface treatments are an ultraviolet treatment, a flame treatment, a corona discharge treatment, and a glow discharge treatment.
A subbing layer provided on the support may have a single layer structure or a double or multi-layer structure. Binders for the subbing layer include copolymers of the monomers such as vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc.; polyethylene-imine, epoxy resins, grafted gelatin, nitrocellulose, and gelatin. Compounds swelling the support include resorcin and p-chlorophenol. Gelatin hardening agents for the subbing layer include chromium salts (e.g., chromium alum), aldehydes (e.g., formaldehyde or glutaraldehyde), isocyanates, active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), epichlorohydrin resins, and active vinylsulfone compounds. The subbing layer may contain fine inorganic particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 µm) as matting agent.
Antistatic agents are preferably used in the present invention. Useful antistatic agents include polymers containing a carboxylic acid or a salt thereof or a sulfonate, cationic polymers, and ionic surfactants. The most suitable antistatic agent is fine particles of at least one crystalline metal oxide selected from ZnO, TiO₂, SnO₂, Al₂O₃, In₂O₃, SiO₂, MgO, BaO, MoO₃, and V₂O₅ or a complex oxide of the above metals (e.g., with Sb, P, B, In, S, Si, and C) or a sol of fine particles of these metal oxides or complex oxides. The metal oxides or complex oxides have a volume resistivity of not more than 10⁷ Ω·cm, preferably not more than 10⁵ Ω·cm, and a particle size of 0.001 to 1.0 µm. The antistatic agent is preferably incorporated in the light-sensitive material in an amount of 5 to 500 mg/m², more preferably 10 to 350 mg/m². A ratio of the conductive crystalline oxide or complex oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.
The light-sensitive material of the present invention is preferably imparted to slip properties. A lubricant-containing layer is preferably provided on both the light-sensitive layer surface and the back surface. Suitable slip properties are such that the coefficient of kinetic friction ranges from 0.01 to 0.25 as measured by sliding a sample film on stainless steel balls of 5 mm in diameter at a speed of 60 cm/min at 25°C and 60% RH. The above measurement gives substantially the equal results even if the material to be combined in rolling friction is replaced with the light-sensitive layer surface.
Useful lubricants include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, and esters of higher fatty acids and higher alcohols. Examples of the polyorganosiloxanes are polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane, and polymethylphenylsiloxane. The lubricants are preferably added to the outermost layer on the emulsion layer side or a backing layer. Polydimethylsiloxane or esters having a long-chain alkyl group are particularly preferred as lubricant.
The light-sensitive material of the present invention preferably contains a matting agent in either the emulsion layer side or the back side, preferably in the outermost layer of the emulsion layer side. Matting agents used may be either soluble or insoluble in processing solutions. It is preferable to use both in combination. For example, particles of polymethyl methacrylate, a methyl methacrylate/methacrylic acid copolymer (9/1 or 5/5 by mole) or polystyrene are preferred. A preferred particle size of the matting agent is 0.8 to 10 µm. The particles preferably have such a narrow size distribution that 90% or more of the number of the total particles have their particle diameter falling within a range of from 0.9 to 1.1 times the mean particle diameter. It is also preferable to use fine particles of 0.8 µm or smaller in combination. Examples of such fine particles are polymethyl methacrylate fine particles of 0.2 µm, methyl methacrylate/methacrylic acid copolymer particles (9/1 by mole) of 0.3 µm, polystyrene resin particles of 0.25 µm, and colloidal silica of 0.03 µm.
The cartridge which can be used for the light-sensitive material of the present invention may be made mainly of metal or synthetic plastics. Preferred plastic materials include polystyrene, polyethylene, polypropylene, and polyphenyl ether. The cartridge for use in the present invention may contain various antistatic agents, such as carbon black, metal oxide fine particles, and nonionic, anionic, cationic or betaine surfactants or polymers. Cartridges thus prevented from static electrification are described in JP-A-1-312537 and JP-A-1-312538. A preferred surface resistivity of the cartridges is not more than 10¹² Ω at 25°C and 25% RH. Plastic cartridges are usually made of plastics having incorporated therein carbon black or other pigments for light shielding. The cartridge may have a currently spread 135 size or may have its diameter reduced from 25 mm (the diameter of 135 size cartridges) to 22 mm or even smaller for small-sized cameras. The cartridge capacity is 30 cm³ or less, preferably 25 cm³ or less. The cartridge and the cartridge case preferably have a total weight of plastic of 5 to 15 g.
The cartridge may be of the type in which a film is advanced by rotating a take-up spool or of the type in which the film leader is put inside the cartridge and let out from the cartridge port by rotating the spool to the film advance direction. These cartridge structures are described in U.S. Patents 4,834,306 and 5,226,613. The photographic films which can be used in the present invention may be either so-called raw films before development or development-processed photographic films. A raw film and a developed photographic film may be put in the same new cartridge or in different cartridges.
The invention will now be illustrated in greater detail by way of Examples, but it should be understood that the invention is not construed as being limited thereto.

EXAMPLE 1

1) Support:

The support used in Example 1 was prepared as follows.
A hundred parts (by weight; hereinafter the same) of polyethylene 2,6-naphthalate (hereinafter abbreviated as PEN) and 2 parts of an ultraviolet absorber Tinuvin P326 (produced by Ciba-Geigy Ltd.) were dried, melted at 300°C, and extruded through a T die. The extruded sheet was stretched longitudinally at 140°C at a stretch ratio of 3.3 and then transversely at 130°C at a stretch ratio of 3.3 and subjected to heat setting at 250°C for 6 seconds to obtain a PEN film having a thickness of 90 µm. Suitable amounts of blue dyes, magenta dyes and yellow dyes (I-1, I-4, I-6, I-24, I-26, I-27, and II-5 described in Technical Disclosure Bulletin 94/6023) were previously added to the PEN film. The PEN film was wound around a stainless steel core of 20 cm in diameter and given a thermal history at 110°C for 48 hours to be rendered resistant against curling.

2) Formation of Subbing Layer:

Both sides of the support were subjected to a corona discharge treatment, a UV discharge treatment, and a glow discharge treatment, coated with a coating composition consisting of 0.1 g/m² of gelatin, 0.01 g/m² of sodium α-sulfo-di-2-ethylhexylsuccinate, 0.04 g/m² of salicylic acid, 0.2 g/m² of p-chlorophenol, 0.012 g/m² of (CH₂=CHSO₂CH₂CH₂NHCO)₂CH₂, and 0.02 g/m² of a polyamide-epichlorohydrin polycondensate to a coating thickness of 10 cc/m² by means of a bar coater to form a subbing layer, on which a light-sensitive layer would be formed later, on the side which had been exposed to a heating temperature at the time of stretching, and dried at 115°C for 6 minutes. All the rollers and transfer unit in the drying zone were set at 115°C.

3) Formation of Backing Layers:

An antistatic layer, a magnetic recording layer, and a slip layer having the composition described below were provided in this order on one side of the support having the subbing layer.

3-1) Formation of Antistatic Layer:

A composition consisting of 0.2 g/m² of a dispersion of fine particles of tin-antimony double oxide having an average particle size of 0.005 µm and a volume resistivity of 5 Ω·cm (secondary particle size: about 0.08 µm), 0.05 g/m² of gelatin, 0.02 g/m² of (CH₂=CHSO₂CH₂CH₂NHCO)₂CH₂, 0.005 g/m² of polyoxyethylene (n=10) p-nonylphenol and resorcin was applied.

3-2) Formation of Magnetic Recording Layer:

A composition consisting of 0.06 g/m² of cobalt-γ-iron oxide coated with 15 wt% of 3-polyoxyethylene(n=15)-propyloxytrimethoxysilane (specific surface area: 43 m²/g: major axis: 0.14 µm; minor axis: 0.03 µm; saturation magnetization: 89 emu/g; Fe⁺²/Fe⁺³=6/94; the surface of the magnetic particles had been treated with 2 wt%, based on iron oxide, of alumina and silica), 1.2 g/m² of cellulose diacetate (the iron oxide powder was dispersed by means of an open kneader and a sand mill), 0.3 g/m² of a hardening agent C₂H₅C(CH₂OCONH-C₆H₃(CH₃)NCO)₃, and solvents (acetone, methyl ethyl ketone, and cyclohexanone) was applied with a bar coater to form a magnetic recording layer having a thickness of 1.2 µm. To the coating composition were added silica particles (0.3 µm) as a matting agent and 3-polyoxyethylene(n=15)-propyloxytrimethoxysilane (15 wt%)-treated alumina (0.15 µm) as an abrasive each in a coated amount of 10 mg/m². The coating layer was dried at 115°C for 6 minutes. All the rollers and transfer unit in the drying zone were set at 115°C. The increase in color density D^B due to the magnetic recording layer as measured with X-Rite (blue filter) was about 0.1. The magnetic recording layer had a saturation magnetization moment was 4.2 emu/g, a coercive force of 7.3 x 10⁴ A/m, and a squareness ratio of 65%.

3-3) Formation of Slip Layer:

A coating composition comprising 25 mg/m² of cellulose diacetate and a (C₆H₁₃CH(OH)C₁₀H₂₀COOC₄₀H₈₁ (compound a; 6 mg/m²)/(C₅₀H₁₀₁O(CH₂CH₂O)₁₆H (compound b; 9 mg/m²) mixture was applied. The compounds a/b mixture was melted at 105°C in a xylene/propylene monomethyl ether mixture (1/1), poured and dispersed in 10 times as much propylene monomethyl ether as the melted mixture of the compounds a/b mixture and the solvents mixture, dispersed in acetone to an average particle size of 0.01 µm, and then added to the coating composition. To the composition were added silica particles (0.3 µm) as a matting agent and alumina (0.15 µm) (coated with 15 wt% of 3-polyoxyethylene(n=15)-propyloxytrimethoxysilane) as an abrasive each in an amount corresponding to a coating weight of 15 mg/m². The coating composition was applied and dried at 115°C for 6 minutes to form a slip layer. All the rollers and transfer unit in the drying zone were set at 115°C. The slip layer exhibited excellent slip characteristics as having a coefficient of kinetic friction of 0.06 (measured with stainless steel ball of 5 mm in diameter under a load of 100 g at a speed of 6 cm/min), a coefficient of static friction of 0.07 (measured by a clip method), and a kinetic friction coefficient of 0.12 with the emulsion layer (hereinafter described).

4) Formation of Light-Sensitive Layer:

On the opposite side of the backing layers, the following layers were provided to prepare a color negative film. The resulting light-sensitive material is designated sample 101.
Main materials used in these layers are classified as follows.
ExC cyan coupler
ExM magenta coupler
ExY yellow coupler
ExS sensitizing dye
UV ultraviolet absorber
HBS high-boiling point organic solvent
H gelatin hardening agent

The amount of each component is given in terms of gram per m², except that the amount of a silver halide is given in terms of gram of silver per m² and the amount of a sensitizing dye is given in terms of mole per mole of silver halide used in the layer where it is added.

1st Layer (Antihalation Layer):
Black colloidal layer	Ag: 0.09
Gelatin	1.60
ExM-1	0.12
ExF-1	2.0 x 10^-3
Solid disperse dye ExF-2	0.030
Solid disperse dye ExF-3	0.040
HBS-1	0.15
HBS-2	0.02

2nd Layer (Intermediate Layer):
Silver iodobromide emulsion M	Ag: 0.065
ExC-2	0.04
Polyethyl acrylate latex	0.20
Gelatin	1.04

3rd Layer (Low-speed Red-sensitive Emulsion Layer):
Silver iodobromide emulsion A	Ag: 0.30
Silver iodobromide emulsion B	Ag: 0.30
ExS-1	6.9 x 10 ^-5
ExS-2	3.0 x 10 ^-5
ExS-3	3.1 x 10 ^-4
ExC-1	0.07
ExC-3	0.130
ExC-4	0.10
ExC-5	0.020
ExC-6	0.010
Cpd-2	0.025
HBS-1	0.10
Gelatin	0.87

4th Layer (Middle-speed Red-sensitive Emulsion Layer):
Silver iodobromide emulsion C	Ag: 0.90
ExS-1	3.5 x 10^-4
ExS-2	3.2 x 10^-5
ExS-3	5.1 x 10^-4
ExC-1	0.09
ExC-2	0.040
ExC-3	0.080
ExC-4	0.090
ExC-5	0.015
ExC-6	0.0070
Cpd-2	0.023
HBS-1	0.10
Gelatin	0.75

5th Layer (High-speed Red-sensitive Emulsion Layer):
Silver iodobromide emulsion D	Ag: 1.60
ExS-1	2.4 x 10 ^-4
ExS-2	2.0 x 10 ^-4
ExS-3	3.4 x 10 ^-4
ExC-1	0.05
ExC-3	0.15
ExC-6	0.020
ExC-7	0.02
Cpd-2	0.050
HBS-1	0.22
HBS-2	0.050
Gelatin	1.10

6th Layer (Intermediate Layer):
Cpd-1	0.090
Solid disperse dye ExF-4	0.030
HBS-1	0.050
Polyethyl acrylate latex	0.15
Gelatin	1.10

7th Layer (Low-speed Green-sensitive Emulsion Layer):
Silver iodobromide emulsion E	Ag: 0.15
Silver iodobromide emulsion F	Ag: 0.10
Silver iodobromide emulsion G	Ag: 0.10
ExS-4	3.0 x 10^-5
ExS-5	2.1 x 10^-4
ExS-6	8.0 x 10^-4
ExM-2	0.33
ExM-3	0.086
ExY-1	0.015
HBS-1	0.30
HBS-3	0.010
Gelatin	0.73

8th Layer (Middle-speed Green-sensitive Emulsion Layer):
Silver iodobromide emulsion H	Ag: 0.80
ExS-4	3.2 x 10 ^-5
ExS-5	2.2 x 10 ^-4
ExS-6	8.4 x 10 ^-4
ExC-8	0.010
ExM-2	0.10
ExM-3	0.025
ExY-1	0.018
ExY-4	0.010
ExY-5	0.040
HBS-1	0.13
HBS-3	4.0 x 10 ^-3
Gelatin	0.80

9th Layer (High-speed Green-sensitive Emulsion Layer):
Silver iodobromide emulsion I	Ag: 1.25
ExS-4	3.7 x 10^-5
ExS-5	8.1 x 10^-5
ExS-6	3.2 x 10^-4
ExC-1	0.010
ExC-6	0.012
ExM-1	0.020
ExM-4	0.025
ExM-5	0.040
Cpd-3	0.040
HBS-1	0.25
Polyethyl acrylate latex	0.15
Gelatin	1.33

10th (Yellow Filter Layer):
Yellow colloidal silver	Ag: 0.015
Cpd-1	0.16
Solid disperse dye ExF-5	0.060
Solid disperse dye ExF-6	0.060
Oil soluble dye ExF-7	0.010
HBS-1	0.60
Gelatin	0.60

11th Layer (Low-speed Blue-sensitive Emulsion Layer):
Silver iodobromide emulsion J	Ag: 0.09
Silver iodobromide emulsion K	Ag: 0.09
ExS-7	8.6 x 10^-4
ExC-8	7.0 x 10^-3
ExY-1	0.050
ExY-2	0.22
ExY-3	0.50
ExY-4	0.020
Cpd-2	0.10
Cpd-3	4.0 x 10^-3
HBS-1	0.28
Gelatin	1.20

12th Layer (High-speed Blue-sensitive Emulsion Layer):
Silver iodobromide emulsion L	Ag: 1.00
ExS-7	4.0 x 10 ^-4
ExY-2	0.10
ExY-3	0.10
ExY-4	0.010
Cpd-2	0.10
Cpd-3	1.0 x 10 ^-3
HBS-1	0.070
Gelatin	0.70

13th Layer (1st Protective Layer):
UV-1	0.19
UV-2	0.075
UV-3	0.065
HBS-1	5.0 x 10^-2
HBS-4	5.0 x 10^-2
Gelatin	1.8

14th Layer (2nd Protective Layer):
Silver iodobromide emulsion M	Ag: 0.10
H-1	0.40
B-1 (diameter: 1.7 µm)	5.0 x 10^-2
B-2 (diameter: 1.7 µm)	0.15
B-3	0.05
S-1	0.20
Gelatin	0.70

In addition, W-1 to W-3, B-4 to B-6, F-1 to F-17, an iron salt, a lead salt, a gold salt, a platinum salt, a palladium salt, an iridium salt, and a rhodium salt were added to each layer appropriately for the purpose of improving preservability, processability, pressure resistance, antifungal and antibacterial properties, antistatic properties, and coating properties.
In Table 1:-
(1) Emulsions J to L had been reduction sensitized with thiourea dioxide and thiosulfonic acid during grain preparation in accordance with Examples of JP-A-2-191938.
(2) Emulsions A to I had been subjected to gold, sulfur, and selenium sensitization in the presence of the spectral sensitizing dyes described for the respective layer and sodium thiocyanate in accordance with Examples of JP-A-3-237450.
(3) Low-molecular weight gelatin was used in the preparation of tabular grains in accordance with Examples of JP-A-1-158426.
(4) Tabular grains were observed under a high-voltage electron microscope to have dislocation lines as described in JP-A-3-237450.
(5) Grains of emulsion L were double-layered grains having a high iodide content in the inside of the core as described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye:

ExF-2 was dispersed as follows.
In a 700 ml pot mill were put 21.7 ml of water, 3 ml of a 5% aqueous solution of sodium o-octylphenoxyethoxyethoxyethanesulfonate, and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10), and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter: 1 mm) were added thereto. The contents were dispersed for 2 hours by means of a BO type vibration ball mill manufactured by Chuo Koki K.K. The contents were taken out and added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to give a gelatin dispersion of the dye. The dispersed dye particles had an average particle size of 0.44 µm.
In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were prepared. The dispersed dye particles had an average particle size of 0.24 µm, 0.45 µm, and 0.52 µm, respectively. ExF-5 was dispersed by a microprecipitation dispersion method described in Example 1 of EP 549,489A. The dispersed ExF-5 particles had an average particle size of 0.06 µm.

H B S - 1 Tricresyl phosphate H B S - 2 Di-n-butyl phthalate
HBS-4 Tri(2-ethylhexyl) phosphate
The resulting light-sensitive material was slit into a 24 mm wide and 160 cm long strip. Sets of two 2 x 2 mm square perforations 5.8 mm apart were made 0.7 mm below one longer side of the strip at intervals of 32 mm over the whole length of the strip. The thus perforated film strip was put into a plastic film cartridge described in U.S. Patent 5,296,887, Figs. 1 through 7.
The film strip was transported at a speed of 1,000/s, and FM signals were recorded on the magnetic recording layer side between sets of perforations using an in- and output head at a head gap of 5 µm and a number of turns of 2,000.
After recording FM signals, the entire emulsion side was uniformly exposed to light of 1,000 cms, processed according to the following processing procedures, and again put into the plastic film cartridge.
Furthermore, sample 101 was slit into a 35 mm wide strip, and photographs were taken on the film with a camera. The exposed film was processed according to the following procedures at a rate of 1 m²/day for consecutive 15 days (running processing).
The processing was carried out with an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd., which had been modified in such a manner that all the overflow from the bleaching bath was not made to flow into the following bath but discharged into a waste solution tank. The automatic processor FP-360B is equipped with an evaporation correction means described in Technical Disclosure Bulletin 94/4992.

Processing steps and the composition of processing solutions are shown below.

Processing Steps:
Step	Time	Temp.	Rate of Replenishment	Tank Volume
Color development	3'5"	38.0°C	20 ml	17 ℓ
Bleaching	50"	38.0°C	5 ml	5 ℓ
Fixing (1)	50"	38.0°C	-	5 ℓ
Fixing (2)	50"	38.0°C	8 ml	5 ℓ
Washing	30"	38.0°C	17 ml	3.5 ℓ
Stabilization (1)	20"	38.0°C	-	3 ℓ
Stabilization (2)	20"	38.0°C	15 ml	3 ℓ
Drying	1'30"	60°C

Stabilization was conducted in a countercurrent system from (2) to (1). All the overflow of the wash bath was introduced into the fixing bath (2). Fixing bath was also made to flow from (2) to (1) through countercurrent piping. The carry-over of the developer to the bleaching bath, that of the bleaching bath to the fixing bath, and that of the fixing bath to the wash bath were 2.5 ml, 2.0 ml, and 2.0 ml, respectively, per 35 mm (W) x 1.1 m (L). The crossover time between every two tanks was 6 seconds, which was included in the processing time of the preceding bath.
The open area of the processor was 100 cm² for the color developer, 120 cm² for the bleaching bath, and about 100 cm² for other processing solutions.

The composition of each processing solution was as follows.

Color Developer:
	Tank Solution	Replenisher
Diethylenetriaminepentaacetic acid	2.0 g	2.0 g
1-Hydroxyethylidene-1,1-diphosphonic acid	2.0 g	2.0 g
Sodium sulfite	3.9 g	5.3 g
Potassium carbonate	37.5 g	39.0 g
Potassium bromide	1.4 g	0.4 g
Potassium iodide	1.3 mg	-
Disodium N,N-bis(sulfonatoethyl)hydroxylamine	2.0 g	2.0 g
Hydroxylamine sulfate	2.4 g	3.3 g
2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline sulfate	4.5 g	6.4 g
Water to make	1.0 ℓ	1.0 ℓ
pH (adjusted with potassium hydroxide and sulfuric acid)	10.05	10.18

Bleaching Bath:
	Tank Solution	Replenisher
Ammonium (1,3-diaminopropanetetraacetato)iron (III) monohydrate	118 g	180 g
Ammonium bromide	80 g	115 g
Ammonium nitrate	14 g	21 g
Succinic acid	40 g	60 g
Maleic acid	33 g	50 g
Water to make	1.0 ℓ	1.0 ℓ
pH (adjusted with aqueous ammonia)	4.4	4.0

Fixing Bath:
	Tank Solution	Replenisher
Ammonium methanesulfinate	10 g	30 g
Ammonium methanethiosulfonate	4 g	12 g
Ammonium thiosulfate (700 g/ℓ aqueous solution)	280 ml	840 ml
Imidazole	7 g	20 g
Ethylenediaminetetraacetic acid	15 g	45 g
Water to make	1.0 ℓ	1.0 ℓ
pH (adjusted with aqueous ammonia and acetic acid)	7.4	7.45

Wash Bath:

Tap water was passed through a mixed bed column packed with an H type strongly acidic cation exchange resin (Amberlite IR-120B, produced by Rohm & Haas Co.) and an OH type strongly basic anion exchange resin (Amberlite IR-400, produced by Rohm & Haas Co.) to reduce calcium and magnesium ion concentrations both to 3 mg/ℓ or less. Then, 20 mg/ℓ of sodium dichloroisocyanurate and 150 mg/ℓ of sodium sulfate were added thereto. The wash bath had a pH of 6.5 to 7.5.

Stabilization Bath:

The tank solution and the replenisher had the same composition.

Sodium p-toluenesulfinate	0.03 g
Polyoxyethylene-p-monononyl phenyl ether (degree of polymerization: 10)	0.2 g
Disodium ethylenediaminetetraacetate	0.05 g
1,2,4-Triazole	1.3 g
1,4-Bis(1,2,4-triazol-1-ylmethyl)piperazine	0.75 g
1,2-Benzoisothiazolin-3-one	0.10 g
Water to make	1.0 ℓ
pH	8.5

Preparation of Samples 102 to 111:

Samples 102 to 111 were prepared in the same manner as for sample 101 except that the compound shown in Table 2 below was added to the 3rd, 4th and 5th layers in an amount of 0.4 mmol/m², 0.2 mmol/m², and 0.3 mmol/m², respectively.
Comparative compounds Cx-A and Cx-B are shown below. Comparative Compound Cx-A (disclosed in U.S. Patent 5,188,926):
Comparative Compound Cx-B (disclosed in U.S. Patent 5,192,646):
Samples 101 to 111 were evaluated as follows.

Residual Sensitizing Dyes:

Each sample was exposed and processed as described above. Residual sensitizing dyes (ExS-1, ExS-2, and ExS-3) were extracted from the unexposed area (i.e., the area having the minimum density) and quantitatively determined by liquid chromatography to obtain a percent retention in terms of a ratio of the total mole number of the residual sensitizing dyes to that of the sample which was not development-processed.

Variation of Photographic Properties from Photographing till Development Processing:

Two strips of each sample were wedgewise exposed to white light. One strip was preserved at 50°C and 60% RH, while the other in a freezer (-20°C), for 6 days and then development-processed as described above.
The difference between the sensitivity of the strip having been preserved at 50°C and 60% RH and that of the strip having been preserved in a freezer was obtained as a measure of variation of photographic properties with time from photographing till development processing. The closer to zero the difference, the smaller the variation. The sensitivity was obtained as a logarithm of a reciprocal of the exposure providing a density of (the minimum density + 0.6).

The results of evaluation are shown in Table 2.

Sample No.	Compound Added	Retention of Total Sensitizing Dyes	Change of Photographic Properties with Time	Remarks
		(%)
101	-	82	+0.04	comparison
102	comparative compound Cx-A	58	+0.12	comparison (U.S. Patent 5,188,926)
103	comparative compound Cx-B	62	+0.10	comparison (U.S. Patent 5,192,646)
104	compound (7)	42	+0.02	invention
105	compound (8)	39	+0.02	"
106	compound (9)	44	+0.03	"
107	compound (10)	32	+0.00	"
108	compound (11)	42	+0.02	"
109	compound (12)	33	+0.00	"
110	compound (40)	50	-0.01	"
111	compound (51)	38	-0.01	"
112	compound (54)	44	-0.01	"
113	compound (57)	48	-0.01	"

It is seen from Table 2 that the samples containing comparative compound Cx-A or Cx-B show reduction of residual sensitizing dyes but undergo considerable change in cyan image sensitivity with time from exposure till development processing, while the samples containing the compound of the present invention show reduction of residual sensitizing dyes and also undergo little variation in photographic properties with time after exposure till development processing.

EXAMPLE 2

Without being exposed, the samples prepared in Example 1 were subjected to development processing in the same manner as in Example 1. After a part of the processed sample was irradiated with light of a fluorescent lamp (20000 lx, 24 hours), the magenta density of the irradiated part (M) and the magenta density of the non-irradiated part (M0) were measured. From the results obtained, the difference in density between the irradiated part and the non-irradiated part, i.e., (M0 - M) was calculated. The larger this density difference, the greater the decrease in density when irradiated light. Large density difference is not preferable in view of photographic properties. The results obtained are shown in Table 3, where the values are in relavive value when the difference of Sample 101 is 1.00.

Sample No. Relative value of (M0 - M) Remarks

101 1.00 Comparison

110 0.63 Invention

111 0.65 "

112 0.65 "

113 0.67 "

Claims

Use of a compound represented by formula (I):
wherein R¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; R² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic group, or a compound selected from

for reducing residual sensitizing dyes after development processing of a silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer.
The use of a compound represented by formula (I) according to claim 1, characterized in that image information obtained after development processing of said silver halide color photographic material is used by irradiating light to the developed photographic material to thereby read the image information optically, and converting the image information to an electric signal.
The use of a compound represented by formula (I) according to claim 1 or 2, characterized in that said silver halide color photographic material has a magnetic recording layer containing magnetic particles on the support on the opposite side to said emulsion layer.
The use of a compound represented by formula (I) according to claim 1, characterized in that R¹ is preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
The use of a compound represented by formula (I) according to claim 1, characterized in that R² is preferably a substituted or unsubstituted alkyl group having 8 to 22 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.