DE69714829T2 - Heat-developable photosensitive material and method of making color images - Google Patents

Abstract

The present invention provides a heat-developable light-sensitive material having a support and a light-sensitive layer provided on the support. The heat-developable light-sensitive material contains dyes which are decolorized through reaction with a decolorizing agent during a development process. The dyes are non-diffusible and at least a part of decolorized dyes resulting from the development process is non-diffusible. Also provided is an image forming method using the heat-developable light-sensitive material. The present method provides images having excellent sharpness within a short period of time.

Description

BACKGROUND OF THE INVENTION 1. Field of the invention

The present invention also relates to a method for producing color images, which provides excellent color differences and sharpness.

The present invention further relates to a method for the instantaneous and rapid production of color images by a heat development process.

2. Description of the state of the art

A silver halide photosensitive material is characterized by high photosensitivity and by providing high-resolution images. Due to the use of processing solutions having a complex composition, a development process for this material involves a negative impact on the environment and involves complicated control of the solution. In recent years, heat-developable Kodachrome type photosensitive materials have been developed and sold which can instantly and quickly form high-quality color images by using a small amount of water and applying heat without using developing processing solutions, as well as image-forming devices which can use such photosensitive materials (PICTROGRAPHY 2000 and 3000 and PICTROSTAT 100 and 200 manufactured by Fuji Photo Film Co., Ltd.). Furthermore, heat-developable silver salt diffusion type photosensitive materials are described in Japanese Patent Application Laid-Open (JP-A) Nos. 62-283332 and 63-198050. However, it has been found that images formed from these diffusion dyes or silver do not have sufficiently satisfactory sharpness in certain uses such as color negatives and intermediate materials for plate making.

In the meantime, colloidal silver or filter dyes have been used for the purpose of improving color discrimination and sharpness. However, since colloidal silver forms fog nuclei, it must be isolated from a silver halide emulsion layer, thus resulting in an increase in the total layer thickness due to the use of an additional intermediate layer(s). Therefore, the effect of using colloidal silver is considerably reduced. Filter dyes which are conventionally used are eluted in a processing solution or cause decolorization. When such filter dyes are applied to a heat-developable photosensitive material, they are transferred to a dye-fixing material together with the image-forming dyes, or cause contamination of images due to insufficient decolorization. Furthermore, in a system in which a photosensitive material is heat-developed with a small amount of water applied thereto, water-soluble dyes, if used, are eluted in the water and contaminate the water. As a result, the water cannot be reused.

An image forming method which solves the above problems is disclosed in JP-A No. 6-337511. In this method, water-insoluble organic pigments are dispersed in a photosensitive material in the form of solid fine grains, and the photosensitive material is heat-developed in the presence of water. Since no organic pigments are transferred to a dye fixing material, color images are not contaminated. However, when a certain sharpness as described above is to be achieved, transferred images or decals are not suitable, and there is no choice but to use the images formed on the photosensitive material. This is not preferred because water-insoluble organic pigments remain on the photosensitive material.

To solve the above problem, a method for forming images by using solid disperse dyes is disclosed in JP-A No. 8-101487. However, it has been found that this method involves the following problems: parts of the dyes are dissolved and move during storage of a light-sensitive material; and the reactivity between couplers and color developing agents is destroyed.

JP-A No. 9-146247 discloses a system in which substances color-developed by leuco dyes and color developers are decolorized by alkali during a development process. This system provides excellent decolorization, but requires a large amount of color developers. Furthermore, this system consumes alkali, so that the reactivity between the couplers and the color developing agents is destroyed.

For simple, rapid processing without the use of processing solutions or with a minimum use of processing solutions, the present inventors have studied a method in which an exposed photosensitive material is used while it is not fixed. As a result, it was found that this method involved the following problems: the color difference from green light and red light to blue light is insufficient due to the insufficient difference between the intrinsic sensitivity of the silver halide contained in a blue photosensitive layer and that of a green photosensitive layer and a red photosensitive layer; the sharpness is deteriorated due to halation during photographing; and the image quality is deteriorated due to the optical scattering caused by the remaining silver halide. In order to solve these problems, the present inventors have found a method in which dyes having a certain structure are introduced into a light-sensitive material and in addition a silver halide emulsion is used which contains tabular grains having (100) and (111) main faces with a high silver chloride content.

A silver halide photographic light-sensitive material must have a high sensitivity. The sensitivity is effectively increased by increasing the sensitivity of the silver halide grains or the amount of use of the silver halide.

As a method of applying the advantage of rapid development of a high silver halide emulsion to a photographic light-sensitive material, a method of using a high silver chloride (100) major face tabular grain emulsion in a photographic light-sensitive material is disclosed in U.S. Patent Nos. 5,264,337, 5,292,632 and 5,310635 and WO 94/22,054. A high silver chloride emulsion was used to achieve a high development speed, and the same processing solutions can be used to process photographic photosensitive materials as well as photosensitive printing materials. However, these publications do not mention the introduction of certain dyes into a photosensitive material.

According to Japanese Patent Application Publication (JP-B) No. 7-120014, a heat-developable photosensitive material exhibits high sensitivity and less fogging due to the use of silver halide grains having (100) major faces and having such a shape that the length of one side is at least twice or at most 0.5 times an arithmetic mean of the lengths of the other two sides. However, these methods do not provide improved image quality, particularly improved sharpness.

Tabular silver chloride grains having (100) major faces are also described in various other publications; e.g., US Patent No. 5,314,798, EP-534,395A, EP-617,321A, EP-617,317A, EP-617,318A, EP-617,325A, WO 94/22,051, EP-616,255A, US Patent Nos. 5,356,764, 5,320,938 and 5,275,930.

Tabular grains with (111) major faces are described in various publications, e.g., in U.S. Patent No. 4,439,520. U.S. Patent No. 5,250,403 describes very thin tabular grains with an average circular diameter of at least 0.7 µm and a thickness of no more than 0.07 µm. Furthermore, U.S. Patent No. 4,435,501 discloses a process for the epitaxial growth of a silver salt on the surfaces of the tabular grains. Furthermore, methods for improving the performance of tabular grains are described in EP- 0,699,947A, EP-0,699,951A, EP-0,699,945A, EP-0,701,164A, EP-0,699,944A, EP-0,701,165A, EP-0,699,948A, EP-0,699,946A, EP-0,699,949A and EP-0,699,950A. These publications disclose methods relating to silver bromide and silver iodobromide, but do not mention silver halide grains of silver chloride having (111) major faces. Furthermore, the action and effect of dyes with a certain structure in the case where these dyes are used in light-sensitive materials is not mentioned.

EP-A-479167 discloses a heat-developable dye diffusion transfer type photosensitive color material comprising a support and a non-transferable filter dye in a photosensitive layer. EP-A-502508 discloses a dye diffusion transfer photographic material comprising a non-diffusible filter dye.

Meanwhile, it is observed that in a light-sensitive material containing processing agents, dyes, if included, prolong the development time. This is because the dyes consume the alkali for their dissociation. Consequently, in some cases it is difficult to incorporate a sufficient amount of dyes into a light-sensitive material.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a method for producing color images with excellent sharpness in a short period of time.

To achieve the object, the present invention provides:

1. A method for producing a color image comprising the steps of performing double-sided adhesion between a heat-developable photosensitive material and a processing material containing a decolorizing agent or a precursor thereof in the presence of water after or simultaneously when the heat-developable photosensitive material is imagewise exposed;

applying heat to the adhered heat-developable photosensitive material and the processing material;

and separating the heat-developable photosensitive material from the processing material, thereby obtaining a color image on the heat-developable photosensitive material and causing decolorization of the dyes;

wherein the heat-developable photosensitive material comprises a support and a photosensitive layer provided on the support, wherein the heat-developable photosensitive material contains dyes which are decolored by a reaction with a decolorizing agent at the time of the development process, the dyes being non-diffusible and at least a part of the decolored dyes resulting from the development process being non-diffusible.

2. Process according to 1, wherein the dyes have neither a carboxyl group nor a sulfo group in their molecules.

3. The method according to 1. or 2., wherein the heat-developable photosensitive material further contains a decolorizable color layer formed from a dispersion in which oil droplets formed by dissolving at least one of the dyes in oil and/or an oil-soluble polymer are dispersed in a hydrophilic binder.

4. The process according to any one of 1. to 3., wherein the dyes are represented by the following formulas (I) to (IV):

A51 = L51 - (L52 = L53)m51 - Q51 (I)

A51 = L51 - (L52 = L53)n51 - A52 (II)

A51 (= L51 - L52)p51 = B 51 (III)

(NC)2C = C(CN) - Q51 (IV)

where "=" represents a double bond and "-" represents a single bond;

each of A51 and A52 represents an acidic ring and B51 represents a basic ring;

Q51 represents an aryl group or a heterocyclic group;

each of L51, L52 and L53 represents a methine group which may have a substituent, wherein the substituents may be linked together to form a 5- or 6-membered ring;

m51 represents 0,1 or 2;

each of n51 and p51 represents 0, 1, 2 or 3;

when a plurality of L51, a plurality of L52 or a plurality of L53 are present in the molecule, the elements of each of the L51, L52 and L53 may be identical to or different from each other;

provided that the compounds represented by formulae (I) to (IV) do not have a carboxyl group or a sulfo group, that the compounds represented by formulae (I) to (IV) have a non-diffusible group, that the resulting products after a development process (decolorization) are also non-diffusible and that they are not substantially eluted from the photosensitive material, and that the compounds represented by formulae (I) to (IV) do not have a group which initiates a redox reaction during the development process and subsequently undergoes bond cleavage to divide into a plurality of molecules.

5. The process according to 4, wherein each of the acidic rings A51 and A52 is a cyclic ketomethylene compound or a compound having a methylene group arranged between two electrophilic groups.

6. The process according to 5, wherein the cyclic ketomethylene compound is 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one, or pyrrolin-2-one; and wherein the compound having a methylene group disposed between electrophilic groups is a group represented by Z51-CH₂-Z52, wherein each of 251 and 252 independently is -CN,

-SO2 R51, -COR51, -COOR51, -CON(R52)2 , -SO2 N(R52)2 , -C[=C(CN)2 ]R51 or

-C[C(CN)₂]N(R51)₂; R51 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R 52 represents a hydrogen atom or groups indicated for R51; wherein R51 and R52 may have a substituent, and wherein, when a plurality of R51 or a plurality of R52 are present, they may be identical to or different from each other.

7. The process according to any one of 4 to 6, wherein the basic ring B51 is pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzoimidazole, benzothiazole, oxazoline, naphthoxazole, or pyrrole.

8. The method according to any one of 1 to 7, wherein the photosensitive layer contains photosensitive halide grains.

9. The method according to 8., wherein the photosensitive layer contains a developing agent and a coupler.

10. The method according to any one of 1 to 9, wherein the photosensitive layer of the heat-developable photosensitive material contains a developing agent, and the processing layer of the processing material contains a base and/or a base precursor (which may be the same or different from the decolorizing agent or a precursor thereof), and wherein the surface of the photosensitive layer of the heat-developable photosensitive material is adhered to the surface of the processing layer of the processing material, water is applied to the surface of the photosensitive layer and/or the surface of the processing layer, followed by heat development.

11. The process according to any one of items 1 to 10, wherein the dyes are contained in an amount of 0.005 to 2 mmol per m² of the heat-developable photosensitive material.

12. The method according to any one of items 1 to 10, wherein the decolorizing agent or a precursor thereof is contained in the heat-developable light-sensitive material in an amount of 0.1 to 200 times the amount of the dyes.

13. The method according to any one of 1 to 7 and 10 to 12, wherein at least one photosensitive layer contains a binder, and a compound which undergoes a coupling reaction with the photosensitive silver halide grains and an oxidation product of a developing agent to form a dye, and wherein after exposure, the surface of the photosensitive layer of the heat-developable photosensitive material is adhered to the surface of the processing layer of the processing material containing a decolorizing agent or a precursor thereof, followed by heat development to form color images, the heat-developable photosensitive material further characterized by containing at least one photosensitive layer:

i) an emulsion containing silver halide grains comprising at least 50 mol% silver chloride, wherein tabular grains having (100) major faces form at least 50% of the projection area, wherein each grain has a rectangular projection area with an adjacent edge ratio of 1:1 to 1:2 and an aspect ratio of at least 2, or

ii) an emulsion containing silver halide grains comprising at least 50% silver chloride, wherein tabular grains having (111) major faces form at least 50% of the projected area, each grain having a hexagonal projected area with an adjacent or contiguous edge ratio of 1:1 to 1:10 and an aspect ratio of at least 2.

BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENTS

First, dyes to be used in the present invention, which are decolored by a reaction with a decolorizing agent at the time of a developing process, are described.

The dyes to be used in the present invention are characterized by decolorization caused by reaction with a decolorizing agent at the time of a development process as well as by no diffusion. The dyes are further characterized in that after being decolorized in a development process, at least a part of the dyes remains non-diffusible. By using such dyes, a photosensitive material has excellent storability, provides images with excellent sharpness and graininess and is capable of being processed in a simple and rapid manner. Furthermore, the photosensitive material does not emit a substance which would otherwise pose a burden on the environment.

Specific examples of such dyes may include cyanines, merocyanines, oxonols, allylidenes (including heteroallylidenes), anthraquinones, triphenylmethanes, azo dyes and azomethine dyes.

Preferably, the dyes used in the present invention have neither a carboxyl group nor a sulfo group in their molecules. The presence of these groups deteriorates the storability and sensitivity of the photosensitive material and the graininess and sharpness of images, and leads to a deteriorated surface state of the photosensitive material and a hardware problem due to the dyes or the decomposed products thereof appearing on the surface of a photosensitive material during a development process.

The dyes to be used in the present invention will now be described in detail.

When a substituent in a dye compound used in the present invention contains an alkyl moiety, an alkenyl moiety, an alkylene moiety or a cycloalkyl moiety, these moieties may be either straight or branched and may be either substituted or unsubstituted.

When a substituent in a dye compound used in the present invention contains an aryl moiety, the aryl moiety may be either unsubstituted or substituted and may be either a monocyclic ring or a condensed ring, unless otherwise specified.

When a substituent in a dye compound used in the present invention comprises a heterocyclic moiety, the heterocyclic moiety may be either unsubstituted or substituted and may be either a monocyclic ring or fused ring, unless otherwise specified.

In the present invention, a heterocyclic ring is preferably a three- to eight-membered ring formed from non-metallic elements, particularly preferably a five- to six-membered ring formed from non-metallic elements.

Preferred non-metallic elements are carbon, oxygen, nitrogen and hydrogen and particularly preferred non-metallic elements are carbon, hydrogen and nitrogen.

Examples of the preferable substituents in the aforementioned moieties may include a halogen atom, an alkyl group, an alkylene group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an aliphatic oxy group, an aryloxy group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamide group, an aliphatic sulfonyl group, and an arylsulfonyl group.

Examples of preferred dyes which can be used in the present invention include compounds represented by the following formulas (I) to (IV):

Formula 1 (I)

A51 = L51 - (L52 = L53)m51 - Q51

Formula (II)

A51 = L51 - (L52 = L53)n51 - A52

Formula (III)

A51 (= L51 - L52)p51 = B51

Formula (IV)

(NC)₂C = C(CN) - Q51

wherein "=" represents a double bond and "-" represents a single bond; each of A51 and A52 represents an acidic ring; B51 represents a basic ring; Q51 represents an aryl group or a heterocyclic group; each of L51, L52 and L53 represents a methine group; m51 represents 0, 1 or 2; each of n51 and p51 represents 0, 1, 2 or 3; wherein, when a plurality of L51, L52 or L53 exist, the substances of each of L51, L52 or L53 may be identical to or different from each other. The compounds represented by formulas (I) to (IV) have no carboxyl group and no sulfo group, but have a non-diffusible group. Compounds formed by a development process (decolorization) also have a non-diffusible property and do not substantially elute from the photosensitive material. The compounds represented by formulas (I) to (IV) do not have such a group that causes a redox reaction during the development process and subsequently undergoes bond cleavage to divide into a plurality of molecules.

Of the acidic rings represented by A51 or A52, a cyclic ketomethylene compound or a compound having a methylene group disposed between electrophilic groups is preferred. Examples of cyclic ketomethylene compounds may include 2-pyrazolin-5-one, 1,2,3,6-tetrahydropyridine-2,6-dione, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolinedione, 2,5-dihydrofuran-2-one and pyrrolin-2-one. Each of these may have a substituent. Among these, preferred compounds are 2-pyrazolin-5-one, 1,2,3,6-tetrahydropyridine-2,6-dione, isoxazolone, dioxopyrazolopyridine, hydroxypyridine, pyrazolinedione and barbituric acid; 2-pyrazolin-5-one, 1,2,3,6-tetrahydropyridine-2,6-dione, isoxazolone, hydroxypyridine, pyrazolinedione and barbituric acid are particularly preferred.

The compound having a methylene group disposed between electrophilic groups is represented by Z51-CH2-Z52, wherein each of Z51 and Z52 represents -CN, -SO2R51, - COR51, -COOR51, -CON(R52)2, -SO2n(R52)2, -C[=C(CN)2]R51 or -C[=C(CN)2]N(R51)2; R51 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; 52 represents a hydrogen atom or groups indicated for R51; wherein each of R51 and R52 may have a substituent, and wherein, when a plurality of R51 or a plurality of R52 exist, they may be identical to or different from each other. Z51 and Z52 may be identical to or different from each other.

Examples of the basic ring represented by B51 may include pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzoimidazole, benzothiazole, oxazioline, naphthoxazole and pyrrole. Each of these may have a substituent. Preferred compounds among these are indolenine, benzoxazole, benzoimidazole, benzothiazole and pyrrole, with indolenine and benzoxazole being particularly preferred.

Examples of the aryl groups represented by Q51 may include a phenyl group and a naphthyl group. Each of these may contain a substituent which is preferably an electrophilic group. Among these, preferred groups are dialkylamino, hydroxyl, alkoxy and alkyl substituted phenyl, with dialkylamino substituted phenyl being particularly preferred.

Examples of the heterocyclic groups represented by Q51 may include a group consisting of pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolidine, Quinoline, carbazole, phenothiazone, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin and coumarone. Each of these may have a substituent. Among the groups listed, pyrrole and indole are preferred.

Each of the methine groups represented by L51, L52 and L53 may contain a substituent. The substituents may be linked together to form a five- or six-membered ring (e.g. cyclopentene or cyclohexene).

Examples of the substituents of the above-mentioned methine groups may include a sulfonamido group (e.g. methanesulfonamido, benzenesulfonamido and octanesulfonamido), a sulfamoyl group (e.g. sulfamoyl, methylsulfamoyl, phenylsulfamoyl and butylsulfiamoyl), a sulfonylcarbamoyl group (e.g. methanesulfonylcarbamoyl and benzenesulfonylcarbamoyl), an acylsulfamoyl group (e.g. acetylsulfamoyl, pivaloylsulfamoyl and benzoylsulfamoyl), a linear or cyclic alkyl group (e.g. methyl, isopropyl, cyclopropyl, cyclohexyl, 2-ethylhexyl, dodecyl, octadecyl, 2-phenethyl and benzyl), an alkenyl group (e.g. vinyl and allyl), an alkoxy group (e.g. methoxy, octyloxy, dodecyloxy, and 2-methoxyethoxy), an aryloxy group (e.g. phenoxy), a halogen atom (e.g. F, Cl and Br) an amino group (e.g. amino, diethylamino and ethyldodecylamino), an ester group (e.g. ethoxycarbonyl, octyloxycarbonyl and 2-hexyldecyloxycarbonyl), an acylamino group (acetylamino, pivaloylamino and benzoylamino), a carbamoyl group (e.g. B. unsubstituted carbamoyl, ethylcarbamoyl, diethylcarbamoyl and phenylethylcarbamoyl), an aryl group (e.g. phenyl and naphthyl), an alkylthio group (e.g. methylthio and octylthio), an arylthio group (e.g. phenylthio and naphthylthio), an acyl group (e.g. acetyl, benzoyl and pivaloyl), a sulfonyl group (e.g. methanesulfonyl and benzenesulfonyl), a ureido group (e.g. 3-propylureido and 3,3-dimethylureido), a urethane group (e.g. methoxycarbonylamino and butoxycarbonylamino), a cyano group, a hydroxyl group, a nitro group, a heterocyclic group (e.g. a benzoxazole ring, a pyridine ring, a sulforane ring, a furan ring, a pyrrole ring, a morpholine ring, a piperanazine ring and a pyrimidine ring).

The dye used in the present invention may preferably be a compound represented by formulas (I), (II), or (III), particularly preferably a compound of formula (I) or a compound of formula (III).

The dye represented by formula (I) is generally called an allylidene dye. When the dye represented by formula (I) is a yellow or a magenta dye, the dye is preferably a compound of formula (V):

wherein "=" represents a double bond; "-" represents a single bond; A61 represents an acidic ring; each of L61, L62 and L63 represents a methine group; each of L64 and L65 represents a C1-C4 alkylene group; each of R62 and R63 represents a cyano group, -COOR64, -CONR65R66, -COR64, -SO₂R64 or -SO₂NR65R66; R64 represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group; each of R65 and R66 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group; R61 represents a substituent; m61 represents 0 or 1; n61 represents an integer between 0 and 4 inclusive; and R65 and R66 may be connected to each other to form a ring. When a plurality of L62 or a plurality of L63 exist, the elements of each of L62 and L63 may be identical to each other or different from each other.

The dye represented by formula (V) is described in detail below.

In a compound (dye) represented by the formula (V), m61 is 0 or 1. When m61 is 0, the dye is called a benzylidene dye, which often serves as a yellow dye. When m61 is 1, the dye is called a cynnamylidene dye, which often serves as a magenta dye.

In the present invention, m61 in the formula (V) is preferably 0 and a compound of the formula (V) preferably serves as a yellow dye.

In formula (V), A61 represents an acidic ring which is identical to a ring defined for A51 and A52 in formulas (I) to (III). A61 is preferably 2-pyrazoline-5- on isoxazolone, hydroxypyridine, pyrazolidinedione or barbituric acid, particularly preferably pyrazolidinedione.

Examples of the methine groups represented by L61, L62 and L63 may include the groups defined for L51, L52 and L53 in the formulas (I) to (III). The methine groups are preferably =CR67-, where R67 is an alkyl group having 1 to 10 carbon atoms or one hydrogen atom.

A preferred combination of L61, L62 and L63 is such that L67 in each of L61, L62 and L63 is a hydrogen atom; or R67 in each of L61 and L63 is a hydrogen atom and R67 in L62 is a methyl group. More preferably, R67 in each of L61, L62 and L63 is a hydrogen.

In formula (V), each of L64 and L65 independently represents a C1-C4 alkylene group, preferably a methylene group or ethylene group. L64 and L65 may preferably be identical to each other.

In the formula (V), each of R62 and R63 represents a cyano group, -COOR64, -CONR65R66, -COR64, -SO₂R64 or -SO₂NR65R66. R64 represents an alkyl group (e.g. methyl, ethyl, i-propyl, t-butyl, benzyl, trifluoromethyl, 2-chloroethyl and 2-ethoxyethyl), an alkenyl group (e.g. vinyl, allyl, oleyl), or an aryl group (phenyl, 2- naphthyl, 4-chlorophenyl, 2-methoxyphenyl and 3-dimethylaminophenyl), preferably an alkyl group or an alkenyl group, with a linear unsubstituted alkyl group being particularly preferred.

Each of R65 and R66 independently represents a group defined for R64 or a hydrogen atom, preferably an alkyl group, an aryl group, or a hydrogen atom, with a chained unsubstituted alkyl group or a hydrogen atom being particularly preferred. When each of R65 and R66 is a group other than hydrogen, the carbon number thereof is preferably 1 to 20, particularly preferably 6 to 20, and particularly preferably 8 to 16.

Each of R62 and R63 particularly preferably represents a cyano group, -COOR64 or -CONR65R66, particularly preferably a cyano group or -COOR64 and in particular preferably -COOR64. When each of R64 and R63 is a cyano group, each of L64 and L65 is preferably an ethylene group. When each of R62 and R63 is -COOR64, each of L64 and L65 is preferably a methylene group.

Although R62 and R63 may be identical to each other or different from each other, they may preferably be identical to each other.

In the formula (V), R61 represents a substituent; preferably a group defined for the substituents of a methine group represented by L61, L62 or L63; more preferably an alkyl group, an alkoxy group, a dialkylamino group or an alkoxycarbonyl group; particularly preferably an alkyl group or an alkoxy group; and most preferably a methyl group or a methoxy group.

In formula (V), n61 represents an integer between 0 and 4 inclusive, preferably 0 or 1, and particularly preferably 0. If n61 is 1, R61 may preferably be substituted at the m-position with the amino group.

Specific examples of the dyes are described below, which should not be construed as a limitation on the invention.

(A56) n = 1

(A57) n = 2

(A58) n = 0

(A59) n = 1

(A60) n = 2

(A63) n = 0

(A64) n = 1

(A70) R = Cl

(A71) R = -SCH3

(A72) R = -OC₂H₅

(A73) R = -CH3

A-133 n = 1

A-134 n = 2

Dyes which can be used in the present invention are prepared using or according to the methods described e.g. E.g. in WO88/04794, EP-274,723, EP-276,556, EP-299,435, in US Patent Nos. 2,572,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429 and 4,040,841, in JP-A Nos. 48-68623, 52-92716, 55-155350, 55-155351, 61-205934, 2-173630, 2-230135, 2-277044, 2-282244, 3-7931, 3-167546, 3-13937, 3-206443, 3-208047, 3-192157, 3-216645, 3-274043, 4-37841, 4- 45436, 4-138449 and 5-197077 and JP-A Nos. 6-332112, 7-206824 and 8-20582.

Specific synthesis examples of Compound Nos. A10, A100 and A134, which are typical compounds that can be used in the present invention, are described below. Example of the synthesis route for compound No. A10

An acetonitrile (250 ml) solution of the compound A10-2 (0.52 mol) was cooled to -7°C in an ice-methanol bath, and phosphorus oxychloride (0.55 mol) was added to the solution while maintaining the temperature of the reaction mixture at 15°C or less. Then, an acetonitrile (250 ml) solution of the compound A10-1 (0.5 mol) was added dropwise to the resulting solution while maintaining the internal temperature at 5°C or less. The cooling bath was removed and the mixture was stirred for an additional hour. The reaction mixture was poured into ice water (1 liter), and an aqueous solution (water: 500 ml) of sodium hydroxide (100 g) was added thereto. The reaction mixture was subjected to two-fold extraction with ethyl acetate (500 ml). The organic layer was washed with brine and concentrated. Recrystallization of the residue from methanol gave compound No. A10-3 (yield 49%).

Compound No. A10-3 (0.05 mol), Compound No. A10-4 (0.05 mol) and potassium carbonate (0.10 mol) were reacted in N,N-dimethylacetamide (200 mL) at 100 °C for 3 hours. The reaction mixture was cooled to room temperature, mixed with ethyl acetate (200 mL) and filtered to remove insoluble matter. The filtrate was washed with 2 N hydrochloric acid, water and brine and concentrated to obtain Compound No. A10-5 quantitatively.

Compound No. A10-5 (0.03 mol) and Compound No. A10-6 (0.03 mol) were refluxed in ethanol (80 mL) for five hours. After the solvent was removed by distillation, the residue was purified by silica gel chromatography (gradient of eluent: methylene chloride/hexane = 4/1 to 1/0) to obtain Compound No. A10 (yield 76%). Synthesis of compound A-100

Bromoacetic acid (a) (76.4 g, 0.55 mol), dodecanol (b) (93.2 g, 0.5 mol) and p-toluenesulfonic acid monohydrate (1.4 g) were dissolved in toluene (200 mL). The mixture was refluxed for 1 hour while the water formed was azeotropically removed, followed by washing three times with 2% aqueous solution of sodium carbonate, dehydration with magnesium sulfate and concentration to obtain a transparent ester (c) (yield 100%).

Aniline (21.1 g, 0.227 mol), the above ester (c) (0.5 mol), potassium carbonate (105 g, 0.75 mol) and sodium iodide (11.2 g, 0.075 mol) were dissolved in dimethylacetamide (300 ml) and the resulting mixture was stirred with heat at 80 °C in a nitrogen atmosphere for four hours. After cooling, the mixture was mixed with water and ethyl acetate to separate the organic phase and the water phase. The organic phase was washed twice with water, dehydrated over magnesium sulfate and concentrated to obtain a solution containing aniline (d) as a main component.

Dimethylformamide (300 ml) was stirred under cooling conditions of 10°C or less. Phosphorus oxychloride (69.6 g, 0.454 mol) was added dropwise so that the temperature did not exceed 20°C. The mixture was continuously stirred at 20°C for 30 minutes, to which a solution containing aniline (d) was added. The mixture was stirred at 60°C for one hour. After the mixture was cooled, water (1 liter) and potassium hydroxide (110 g) were carefully added sequentially so as to adjust the pH to 8. The resulting solution was extracted with ethyl acetate. The oil phase was washed twice with water, dehydrated over magnesium sulfate and concentrated. The residue was cooled by adding acetonitrile to form benzaldehyde (e) with pale brown crystals, which were isolated by filtration and washed with cold acetonitrile. The yield of benzaldehyde (e) was 74.2 g (57% based on aniline).

Pyrazolidinedione (f) (6.31 g, 0.025 mol), the above-mentioned benzaldehyde (e) (15.8 g, 0.275 mol) and acetic anhydride (7.7 g, 0.075 mol) were dissolved in ethanol (50 mL), and the mixture was refluxed for two hours. The solution was cooled to precipitate crystals, which were isolated by filtration and washed with cold ethanol to obtain Compound No. A-100 as pale yellow crystals. The yield of compound No. A-100 was 16.4 g (81.2% based on pyrazolidinedione (f)). Synthesis of compound No. A-134

Diketen (347 ml) was added dropwise over 30 minutes to a mixture of Compound No.A134-1 (1020 g), pyridine (24.3 ml), and N,N-dimethylacetamide (2 liters) contained in a three-necked container while stirring the mixture with application of heat (internal temperature: 85 °C). The resulting solution was stirred for further three hours under heat, followed by cooling to room temperature and extracting with ethyl acetate (4 liters) and water (4 liters). The ethyl acetate layer was washed for five times with a mixture of saturated brine (500 ml) and water (2 liters) and dehydrated over sodium sulfate anhydrate. The solution was concentrated in a rotary evaporator, and the resulting residue was mixed with isopropyl alcohol (2.5 liters) to form crystals, which were isolated by filtration, thereby obtaining Compound No.A134-2 (yield 944 g, 74%).

Piperidine (119 ml) was added dropwise over five minutes to a mixture of the above-mentioned compound No. A134-2 (424 g) and isopropyl alcohol (900 ml) in a three-necked container while stirring at room temperature. After the addition was completed, ethyl cyanoacetate (128 ml) was added dropwise over ten minutes to the resulting mixture under reflux with heat. The resulting solution was further stirred under reflux with heat for three hours, followed by cooling to room temperature and extracting with ethyl acetate (2 liters) and water (2 liters). The obtained ethyl acetate phase was washed five times with a wash of saturated brine (300 ml) and water (1 liter) and dehydrated with sodium sulfate anhydrate. The solution was concentrated in a rotary evaporator and the residue was mixed with acetonitrile (1.2 liters). Concentrated hydrochloric acid (129 mL) was added dropwise over 20 minutes to the resulting acetonitrile solution while stirring it in an ice bath. The crystals which precipitated were isolated by filtration to thereby obtain Compound No. A134-3 (yield 393 g, 83%).

Piperidine (202 ml) was added dropwise over 25 minutes to a mixture of the above-mentioned compound No. A134-4 (142 g) and acetonitrile (1.5 liters) in a three-necked container with stirring at room temperature. Then, acetic anhydride (94 ml) was added dropwise over ten minutes to the resulting mixture. After the completion of the addition, the resulting solution was stirred for ten minutes. minutes. Compound No. A134-3 (473 g) was added to the resulting solution over 20 minutes, followed by stirring for three hours and stirring in an ice bath for an additional hour. The crystals that precipitated were isolated by filtration to thereby obtain Compound No. A134 (yield 388 g, 77%).

The structure of each of these compounds was confirmed by NMR, MS spectrum and elemental analysis.

The above-mentioned dyes in the present invention are preferably used in a yellow filter layer, a magenta filter layer, or an antihalation layer, each layer serving as a decolorizing dye layer. Thus, in a case where the photosensitive layers are a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer in this order from the layer directly disposed on the support, a yellow filter layer may be provided between the blue-sensitive layer and the green-sensitive layer; a magenta filter layer may be provided between the green-sensitive layer and the red-sensitive layer, and a cyan filter layer (antihalation layer) may be provided between the red-sensitive layer and the support. The amounts of the dyes are such that the transmission densities of the yellow filter layer, the magenta filter layer, and the antihalation filter layer for blue light, green light, and red light may each be 0.03 to 3.0, more preferably 0.1 to 2.0. In particular, the amount may be 0.005 to 2 mmol/m², more preferably 0.05 to 2 mmol/m², depending on ε and the molecular weight of the dye.

The light-sensitive material used in the present invention may contain two or more dyes in a single layer. Therefore, the above-mentioned antihalation layer may contain a mixture of a yellow dye, a magenta dye and a cyan dye.

The photosensitive layer used in the present invention contains a decolorizing dye. Before the dye is incorporated into the photosensitive material, the dye is preferably dissolved in oil and/or an oil-soluble polymer, and then the oil droplets thus formed are dissolved in a hydrophilic binder dispersed. Preferred methods for preparing the dye dispersions include an emulsion dispersion method described, for example, in U.S. Patent No. 2,322,027. When this method is used, an oil having a high boiling point described, for example, in U.S. Patent Nos. 4,555,470, 4,536,466, 4,587,206, 4,555,476 and 4,599,296 and in JP-B No. 3-62256 may be used, optionally in combination with an organic solvent having a boiling point of 50°C to 160°C. An oil-soluble polymer may be used instead of the oil or in combination with the oil. Some examples of these are described in PCT WO 88/00723. The high boiling point oil and/or the polymer are used in an amount of 0.01 to 10 g, preferably 0.1 to 5 g, per gram of dye used.

Alternatively, the dye may be dissolved in a polymer by a latex dispersion method. Specific examples of the latex used for impregnation in the method are described, for example, in U.S. Patent 4,199,363, German Patent Application Laid-Open (OLS) Nos. 2,541,274, 2,541,230, JP-B No. 53-41091, and EP-029,104.

In order to disperse the oil droplets in a hydrophilic binder, a variety of surfactants can be used. Such surfactants are described, for example, in JP-A No. 58-157636 (page 37 to page 38) and Kochi Gijutsu Volume 5 (published on March 22, 1991 by As-tech Company Ltd., pages 136 to 138). Alternatively, the phosphate ester type surfactants described in JP-A Nos. 7-56267 and 7-228589 and German Patent Application Laid-Open No. 932,299A can be used.

The hydrophilic binder may preferably be a water-soluble polymer. Examples of the water-soluble polymers may include natural compounds such as proteins (e.g. gelatin and gelatin derivatives); polysaccharides such as cellulose derivative, starch, gum arabic, dextrin and pullulan; and synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. These water-soluble polymers may be used in combination of two or more kinds. A combination with gelatin is particularly preferred. Gelatin may be classified among lime-treated gelatin, acid-treated gelatin and so-called decalcified gelatin. with a reduced calcium content, which can be used alone or in combination according to the purpose.

In the present invention, the dyes can be decolorized by reacting with a decolorizing agent in the processing step.

The decolorizing agent or a precursor thereof in the present invention is preferably a nucleophilic agent or a precursor thereof, particularly a base or a precursor thereof.

Examples of the decolorizing agent may include alcohols or phenols (R51OH), amines or anilines ((R52)₃N), hydroxylamines ((R52)₂NOR52), sulfinic acids (R51SO₂H) or their salts, sulfuric acid or their salts, thiosulfuric acid or their salts, carboxylic acid (R51CO₂H) or their salts, hydrazines ((R52)₂NN(R52)₂), guanidines ([(R52)₂N]₂C=NH), aminoguanidines ((R52)₂NR52N(R52N)C=NH), amidines, thiols (R51SH), cyclic or linear active methylene compounds (Z53-CH₂-Z54, where Z53 and Z54 equivalent to Z51 and Z52 and can be linked together to form a ring), and anionic species derived from these compounds.

Preferred among these are hydroxylamines, sulfinic acids, sulfuric acids, guanidines, aminoguanidines, heterocyclic thiols, cyclic or linear active methylene compounds and active methine compounds, with guanidines and aminoguanidines being particularly preferred.

These decolorizing agents may be previously incorporated into photosensitive materials or may be incorporated into the materials at the processing stages by suitable techniques. Alternatively, decolorizing agents may be converted into precursors before they are incorporated into the photosensitive materials.

The above-mentioned decolorizing agents can decolorize the dyes by nucleophilic addition to the dye molecules induced by interaction between them in the processing steps. Preferably, the above-described steps for producing a color image on a silver halide light-sensitive material and for decolorizing the dyes are used in a similar manner: Image-forming Exposing a silver halide photosensitive material containing dyes; laminating a processing material containing a decolorizing agent or its precursor thereon subsequent to or simultaneously with exposure so that their layer surfaces are bonded together; heating; and separating the materials by exfoliation. In this case, the density of the dye after being decolorized is 1/3 or less, preferably 1/5 or less of the initial density. The amount of the decolorizing agent used is 0.1 to 200 times, preferably 0.5 to 100 times the amount of the dye in mol.

The dyes to be used in the present invention are useful in a variety of systems. Preferably, they are used in a system containing a self-contained color developing agent and a coupler. A detailed description of the developing agent and the coupler will be provided later.

The silver halides which can be used in the present invention are silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodidobromide.

The silver halide emulsion used in the present invention may be of the surface latent image type or the internal latent image type. Internal latent image type emulsions, which may be used in combination with nucleating agents or fogging agents, directly serve as reversal emulsions. The internal latent image type emulsions may be of the core/shell type in which the internal portion and the surface portion of an emulsion particle have different phases. Alternatively, silver halides having different compositions may be bonded to each other by epitaxial bonding. The silver halide emulsions may be monodisperse emulsions or multidisperse emulsions. Preferably, as described in JP-A Nos. 1,167,743 and 4-223,463, monodisperse emulsions are mixed with each other so as to adjust the gradation. The grain size is preferably within the range of 0.1 to 2 micrometers, particularly preferably 0.2 to 1.5 micrometers. The crystal habit of the silver halide grains may have a regular crystal form such as cubic, octahedral and tetradecahedral; an irregular crystal form such as spherical or tabular or flat with a high aspect ratio; or have a crystal form with crystal defects such as twin planes; or their combined forms.

Preferred silver halide grains of the present invention are described below.

In the present invention, at least one photosensitive layer contains:

i) an emulsion containing silver halide grains consisting of at least 50 mol% silver chloride, wherein tabular grains with (100) major faces form at least 50% of the projection area, wherein each grain has a rectangular projection area with an adjacent or contiguous edge ratio of 1:1 to 1:2 and an aspect ratio of at least 2; or

ii) an emulsion containing silver halide grains consisting of at least 50 mol% silver chloride, wherein tabular grains having (111) major faces form at least 50% of the projected area, each grain having a hexagonal projected area of an adjacent or contiguous edge ratio of 1:1 to 1:10 and an aspect ratio of at least 2. In the context of the present invention, this is fulfilled if 50% or more of the projected area of the silver halide grains contained in the emulsion satisfy the above requirement. Preferably, not less than 70% of the projected area satisfies the above requirement.

The term "aspect ratio" as used here refers to a value obtained by dividing the diameter of a circle defining an area corresponding to the projection area by the grain thickness.

In a first embodiment of the present invention, the silver halide grains (100) have major outer surfaces. Therefore, the projection area of the grains provides a rectangular shape. It is necessary that the ratio of the adjacent sides of the rectangular projection area is within the range of 1:1 to 1:2.

When an emulsion formed from rod-shaped grains or quasi-cubic rectangular parallel-shaped grains is used, the effect of the present invention cannot be achieved. In the present invention, tabular grains each providing a substantially square-shaped projection area having an adjacent aspect ratio of 1:2 to 1:1.5 are preferred.

In a second embodiment of the present invention, the silver halide grain (111) has main outer surfaces. Therefore, the projection area of the grain provides a hexagonal shape. It is necessary that the ratio of two adjacent sides of the hexagonal projection area falls within the range of 1:1 to 1:10. If an emulsion formed from triangular-shaped grains is used, the effect of the present invention cannot be obtained. In the present invention, tabular grains each providing a substantially regular hexagonal projection area with an adjacent aspect ratio of 1:1 to 1:5 are preferred.

The shape of the silver halide grains can be determined by electron microscopy, by a carbon imprint process in which silver halide grains and latex particles, which serve as reference material for standard sizes, are simultaneously subjected to darkening with heavy metals.

Regarding the halogen composition of the silver halide grains suitable for use in the present invention, the silver chloride is 50 mol% or more based on the content of silver chlorobromide, silver chloroiodide, or silver iodobromide. It is needless to say that silver chloride itself can be used. Although the emulsions may contain silver iodide, the silver iodide content is preferably not less than 2 mol%, particularly preferably not less than 1 mol%. It is also preferred that the silver halide emulsion is formed by grains each having a layered structure having a plurality of intergrain layers of different halogen compositions. Expressed in a projected area corresponding to a circle, the size of the silver halide grains used in the present invention is preferably 0.1 to 10 micrometers, more preferably 0.3 to 5 micrometers, and most preferably 0.5 to 4 micrometers.

To prepare an emulsion used in the present invention, i.e., an emulsion containing silver halide grains comprising at least 50 mol% of silver chloride, wherein tabular grains having (100) major faces constitute at least 50% of the projected area, each grain having a rectangular projected area with an adjacent edge ratio of 1:1 to 1:2 and an aspect ratio of at least 2, or an emulsion containing silver halide grains comprising at least 50 mol% of silver chloride, wherein tabular grains having (111) major faces constitute at least 50% of the projected area, each grain having a hexagonal projected area with an adjacent edge ratio of 1:1 to 1:10 and an aspect ratio of at least 2, a variety of methods including conventionally known ones can be used.

When preparing tabular grain emulsions with (100) major external surfaces having high AgCl content, methods described in, for example, JP-A Nos. 5-204,073, 51-88,017, 63-24,238 and 7-146,522 can be arbitrarily used.

Methods for preparing tabular grain emulsions having (111) main faces with high AgCl content are described, for example, in U.S. Patent Nos. 4,339,215, 4,404,463, and 5,217,858 and JP-A No. 2-32. In the case of high AgCl content emulsions, under conditions where no adsorptive substances are present, (100) faces are generally formed as the faces. Therefore, by using an adsorptive substance that favors the (111) face and by eliminating nuclei of rectangular single twin crystals and non-parallel arranged crystal nuclei during a physical ripening process after the formation of twin crystal nuclei, nuclei of parallel multi-twin face crystals can be obtained selectively. The nuclei thus obtained are allowed to grow to give a light-sensitive silver halide emulsion containing tabular grains. The rule of thumb regarding the formation of tabular silver chloride grains with (111) faces is described in "Journal of Photographic Science", Volume 36, p. 182 (1988).

The critical point in the preparation of tabular grains used in the present invention is to achieve that the nucleus that grows has a tabular shape. In this regard, it is described in the aforementioned publication in connection with manufacturing processes that the addition of iodide ions or bromide ions during the initial stage of grain formation or the addition of a compound showing preferential adsorption on a specific area is effective.

The average grain thickness of the tabular grains used in the present invention is between 0.01 and 0.5 micrometers, preferably between 0.01 to 0.4 micrometers, more preferably between 0.05 to 0.4 micrometers.

The mean grain thickness is an arithmetic mean of the thickness of all tabular grains contained in the emulsion.

In order to form tabular grains with a high aspect ratio, it is important that twin crystal nuclei with a small size are formed. In this regard, a variety of means can be used, including low temperature, high pBr content, low pH, use of a reduced amount of a specific type of gelatin with low methionine content or low molecular weight, or use of a phthalated gelatin derivative, or nucleation in a reduced nucleation time.

After nucleation, tabular grains (parallel multitwin crystal nuclei) are formed by physical ripening alone, so that nuclei of other regular crystals, single twin crystal nuclei or non-parallel twin crystal nuclei are eliminated to selectively form parallel multitwin crystal nuclei. Subsequently, soluble silver salts and soluble halogen salts are added to induce the growth of the grains, resulting in an emulsion formed of tabular grains.

The emulsion formed in the present invention is preferably monodisperse.

The coefficient of variation of the diameter corresponding to a circle of the projected area of all the silver halide grains contained in the emulsion used in the present invention is preferably 30% to 3%, more preferably 25% to 3%, and particularly preferably 20% to 3%. The range above 30% is not preferred in view of the homogeneity of the grains. However, the present invention is not limited by these numerical values.

The coefficient of variation of the circle-corresponding diameter represents a value obtained by dividing the standard deviation of the circle-corresponding diameter of the respective silver halide grains by the average circle-corresponding diameter.

If the grains contain phases containing iodides or chlorides, these phases may be evenly distributed within the grains or arranged locally.

Other silver salts, e.g. silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate and organic acid salts of silver may be present as individual grains or as part of the silver halide grains.

The tabular grains used in the present invention may contain dislocation lines.

A dislocation line is a linear lattice defect that occurs along a boundary between an area that has already shifted and an area that has not yet shifted.

References concerning the dislocation lines of a silver halide crystal include: 1.) C. R. Berry, J. Appl. Phys., 27, 636 (1956); 2.) C. R. Berry, D. C. Skilman, J. Appl. Phys., 35, 2165 (1964); 3.) J. F. Hamilton, Phot. Sci. Eng., 11, 57 (1967); 4.) T. Shiozawa, J. Soc. Phot. Sci. Jap., 34, 16 (1971); 5.) T: Shiozawa, J. Soc. Phot. Sci. Jap., 35, 213 (1972). Dislocation lines can be analyzed by X-ray crystal structure analysis or by a direct observation method using a transmission electron microscope at a low temperature.

If dislocation lines are to be observed directly via a transmission electron microscope, silver halide grains are taken directly from an emulsion, and this is done with particular care so as not to apply too much pressure to generate dislocation lines in the grains, and the grains thus obtained are placed on a grid for observation by an electron microscope and they are observed by the transmission method while they are cooled to avoid damage by the electron beam (like a printout).

In this case, since thicker grains are less easily illuminated by an electron beam, it is desirable to use a high voltage (200 kV or more for a thickness of 0.25 µm) in the electron microscope to obtain a clearer view.

JP-A No. 63-220,238 discloses a method concerning controlled introduction of dislocation lines into the respective silver halide grains.

This paper shows that tabular grains in which dislocation lines have been introduced are superior in their photographic properties, such as sensitivity and reciprocity, compared with tabular grains which do not have dislocation lines.

In the case of tabular grains, the position and number of dislocation lines observed in a direction perpendicular to the major surface can be obtained for each grain by examining the electron micrograph of the grains described above.

The emulsions used in the present invention and other photographic emulsions which are used are described below.

In particular, any of the silver halide emulsions prepared using various methods described, for example, in U.S. Pat. No. 5,442,444 can be used in the present invention. B. in U.S. Patent No. 4,500,626 (column 50), in U.S. Patent No. 4,628,021, in Research Disclosure (hereinafter abbreviated as RD) No. 17,029 (1978), in RD No. 17,643, pp. 22 to 23 (December 1978), in RD No. 18,716, p. 648 (November 1979), in RD No. 307,105, pp. 863 to 865 (November 1989), in JP-A Nos. 62-253,159, 64.13,546, 2-236,546, 3-110,555; and further in P. Grafkides, Chemie et Phisque Photographque, Paul Montel, Paris (1967); G. F. Duffin, in Photographic Emulsion Chemistry, Focal Press, (1966); VL Zelikman et al., in Making and Coating Photographic Emulsion, Focal Press (1964).

In a process for producing the light-sensitive silver halide emulsions used in the present invention, it is preferable to carry out the so-called desalting process, that is, the removal of excess salts from the silver halide emulsions. This removal can be carried out using the noodle washing process which involves gelling the gelatin, or using a flocculation process which takes advantage of a polyvalent anion-containing inorganic salt (such as sodium sulfate), an anionic surfactant, an anionic polymer (such as sodium polystyrene sulfate) or a gelatin derivative (such as an aliphatic acylated gelatin, an aromatic acylated gelatin or an aromatic carbamoylated gelatin). Preferably, a flocculation process is used in the present invention.

The light-sensitive silver halide emulsions used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or as a combination of two or more of them. The amount of the heavy metals added, although it depends on the intended purpose, is generally on the order of 10-9 to 10-3 mol per mol of the silver halide. These metals may be incorporated into the emulsion grains so that their distribution throughout the grains is uniform, or may be located in inner regions or in surface regions of the grains. In particular, the emulsions described, for example, in U.S. Pat. B. Preferably used in JP-A Nos. 2-236,542, 1-116,637 and 4-126,629.

In the step of forming silver halide grains in the light-sensitive silver halide emulsions used in the present invention, a rhodanate, ammonia, a tetrasubstituted thiourea compound, an organic thioether derivative described in JP-B No. 47-11,386, a sulfur-containing compound described in JP-A No. 53-144,319 as a solvent for the silver halides.

For the details of the other conditions, reference may be made to the descriptions in the above-mentioned books, particularly in P. Grafkides, Chemie et Phisque Photographic, Paul Montel (1967); G. F. Duffin, Photographic Emulsion Chemistry, Focal Press, (1966); and V. L. Zelikman et al., Making and Coatina Photographic Emulsion, Focal Press, (1964). In particular, the present silver halide emulsions can be prepared by an acidic method, a neutral method and a basic method. Furthermore, a method suitably used to react a soluble silver salt with a soluble halide may be a single jet method, a double jet method and a combination of these. In order to obtain a monodisperse emulsion, a double jet method is preferably used.

Furthermore, a reverse mixing process in which silver halide grains are produced in the presence of an excess of silver ions can be used. In addition, as a type of double jet process, the so-called controlled double jet process can be used in which the pAg value of the liquid phase from which the silver halide grains are to be precipitated is kept constant.

Furthermore, for the purpose of increasing the rate of grain growth, the concentration, amount and rate of introduction of a silver salt or a halide may be increased (as described in JP-A Nos. 55-142,329, 55-158,124 and US Patent No. 3,650,757).

Furthermore, stirring of a reaction solution can be carried out by any known method. On the other hand, the temperature and pH of a reaction solution during the formation of silver halide grains can be appropriately selected depending on the intended purpose. A suitable pH range is between 2.2 to 8.5, particularly preferably between 2.5 to 6.0.

Photosensitive silver halide emulsions are, in general, chemically sensitized silver halide emulsions. For chemically sensitized photosensitive silver halide emulsions used in the present invention, known chemical sensitization methods for the emulsions of conventional photosensitive materials can be used. Examples of these methods include a chalcogen sensitization method (e.g., a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method), a noble metal sensitization method (using gold, platinum, palladium), and a reduction sensitization method. These methods can be used alone or in combination of two or more (as described, for example, in JP-A Nos. 3-110,555 and 5-241,267). Such chemical sensitization can also be carried out in the presence of a nitrogen-containing heterocyclic compound (as described in JP-A No. 62-253,159). Furthermore, an antifogging agent, which will be mentioned below, can be added after the completion of chemical sensitization. In particular, the addition of an antifogging agent can be carried out in the manners described in JP-A Nos. 5-54,833 and 26-40,446.

The pH value during chemical sensitization is preferably between 5.3 to 10.5, and particularly preferably between 5.5 to 8.5; while the pAg value is preferably between 6.0 to 10.5, and particularly preferably between 6.8 to 9.0.

The coating amount of the photosensitive silver halide used in the present invention is preferably within the range of 1 mg to 10 g, more preferably 0.1 g to 10 g, on a silver basis per square meter of a photosensitive material.

In order to impart color sensitivities including green sensitivity, red sensitivity and infrared sensitivity to the light-sensitive silver halide used in the present invention, the light-sensitive silver halide emulsions are spectrally sensitized with methine dyes or other dyes. Furthermore, if necessary, a blue-sensitive emulsion can be spectrally sensitized in the blue color region.

Suitable dyes that can be used for the above purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styrene dyes and hemioxonol dyes.

Specific examples of such sensitizing dyes are disclosed in U.S. Patent No. 4,617,257, JP-A Nos. 59-180,550, 64-13,546, 5-45,828, 5-45,834.

These sensitizing dyes can be used individually or in combination. In particular, combinations of sensitizing dyes are often used for hypersensitization or for wavelength adjustment of spectral sensitization.

In addition to the sensitizing dyes, other dyes which do not spectrally sensitize the silver halide emulsions themselves or compounds which do not substantially absorb light in the visible region but exhibit a supersensitizing effect can be introduced into the silver halide emulsions (see, for example, U.S. Patent No. 3,615,641 and JP-A No. 63-23,145).

These sensitizing dyes can be added to the silver halide emulsions during, before or after chemical ripening or before or after formation of the nuclei of the silver halide grains according to the descriptions of U.S. Patent Nos. 4,183,756 and 4,225,666. These sensitizing dyes and supersensitizers can be added to the emulsion as a solution in an organic solvent such as methanol, a dispersion in gelatin or a solution containing a surfactant. A suitable amount of each of these ingredients added is generally in the range of 10-8 to 10-2 moles per mole of the silver halide.

Additives used in the aforementioned steps and known photographic additives which can be used in the present invention are described in the aforementioned RD. Nos. 17,643, 18,716 and 307,105, and the areas in which relevant descriptions are given are shown below.

(RC: right column, LC: left column)

In the first and second embodiments of the light-sensitive material to be used in the present invention, the light-sensitive material is constructed such that a layer having a photographic component is provided on a support therefor, the layer having the photographic component comprising at least a photographic light-sensitive layer formed of light-sensitive silver halide, a compound which forms a dye by a coupling reaction with an oxidizing product of a developing agent (the compound is hereinafter referred to as a coupler), and a binder.

In the present invention, color reproduction by a subtraction color method can be basically used to produce a photosensitive material for recording original scenes and reproducing the recorded scenes in the form of color images. That is, at least three photosensitive layers are provided which have different photosensitivities in blue, green and red regions, each of the layers containing a color coupler capable of forming yellow, magenta or cyan dyes which satisfy the relationship a complementary color to their own photosensitive wavelength range, thereby recording the color information relating to the original scenes. Color photographic printing paper having the relationship between the photosensitive wavelengths and the color tones to be developed similar to that of the photosensitive material is exposed to light passed through the color images thus obtained to reproduce the original scenes. Alternatively, the information relating to the color images obtained by photographing the original scenes may be read by means of a scanner, and based on the information thus read, the images may be reproduced for viewing.

The photosensitive material used in the present invention may comprise a photosensitive layer sensitive to light of three or more wavelength regions.

Furthermore, the photosensitive wavelength ranges and color tones to be developed may have relationships other than the above-mentioned relationship of complementary color and photosensitivity. In such a case, the information of the read image may be subjected to image processing such as color conversion so as to reproduce the original color information.

According to the present invention, it is preferable to contain at least two kinds of silver halide emulsions which are sensitive to light of the same wavelength range and have different mean grain boundaries of the projection area. The term "sensitive to light of the same wavelength range" as used in the present invention means "effectively sensitive to light of the same wavelength range." Accordingly, even if emulsions are slightly different in their spectral sensitivity, the emulsions are considered to be sensitive to light of the same wavelength range if their photosensitive ranges significantly overlap.

In this case, the difference in the average protruding grain area between the emulsions is preferably 1.25 times, particularly preferably 1.4 times or more, and most preferably 1.6 times or more. When three kinds or more of emulsions are used This relationship is preferably satisfied between the emulsions with the smallest mean projection area and a largest mean projection area.

According to the present invention, in order to introduce into a photosensitive material a plurality of emulsions which are sensitive to the light of the same wavelength range and have different average projection areas, different photosensitive layers may be provided for the respective emulsions, or alternatively, a single photosensitive layer may be mixed to contain these emulsions.

When these emulsions are contained in individual layers, an emulsion with a larger average projection area is preferably contained in an upper layer (located closer to the incident light source).

When these emulsions are contained separately in respective layers, the color couplers to be combined preferably have the same hue. The photosensitive layers may also have different hues to be developed by mixing the couplers which develop into different hues. Alternatively, couplers with different hue absorbing profiles may be contained in the respective photosensitive layers.

In the present invention, the emulsions sensitive to the light of the same wavelength region are preferably used in such a way that the ratio of the number of silver halide grains per unit area of a light-sensitive material contained in these emulsions becomes larger than the ratio of a value obtained by dividing an amount of silver of an emulsion used by the average projection area of the silver halide grains contained in the emulsion to the power of 3/2 and such a tendency that this tendency is more conspicuous for an emulsion having a larger average projection area. This provides images with good graininess even when development is carried out at high temperatures. Furthermore, good development performance and wide exposure latitude are achieved.

Conventionally, in order to achieve a desired graininess value of a color negative for photographic purposes, not only a silver halide emulsion has been improved, but a so-called DIR coupler which releases a development-inhibiting compound upon coupling reaction with an oxidation product of a developing agent has been used. A light-sensitive material of the present invention provides an excellent graininess value even when no DIR coupler is used, and provides an even better graininess value when a DIR compound is used in combination.

In the present invention, organometallic salts can be used as an oxidizing agent together with the photosensitive silver halide. Among these organometallic salts, organic silver salts are particularly preferred.

Examples of the organic compounds which can be used for preparing the above-mentioned organic silver salts serving as oxidizing agents include benzotriazoles, fatty acids and other compounds described in U.S. Patent No. 4,500,626, columns 52 to 53. The silver acetylide described in U.S. Patent No. 4,775,613 is also suitable. These organic silver salts can be used alone or in a combination of two or more of them.

The organic silver salts can be used in an amount between 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of the photosensitive silver halide. The total weight of the photosensitive silver halide and the organic silver salt used for coating is in the range of 0.05 to 10 g/m², preferably 0.1 to 4 g/m², based on the weight of the silver.

The binder for a constituting layer of the photosensitive material is preferably a hydrophilic material, examples of which include those described in the aforementioned RD, and those described on pages 71 to 75 in JP-A No. 64-13546. Specifically, the binder is preferably a transparent or translucent hydrophilic binder exemplified by a naturally occurring compound such as a protein comprising gelatin, and a gelatin derivative; and polysaccharides comprising a cellulose derivative, starch, gum arabic, dextran and pullulan, as well as a synthetic polymer such as polyvinyl alcohol, polyvinylpyrrolidone and acrylamide polymer. As the binder, a highly water-absorbent polymer described in U.S. Patent No. 4,960,681 and JP-A No. 62-245,260 is also suitable. Specifically, such polymers are homo- or copolymers of vinyl monomers with -COOM or -SO₃M (where M represents a hydrogen atom or an alkali metal), and copolymers of a vinyl monomer with the above group and other vinyl monomers (e.g., such as sodium methacrylate and ammonium methacrylate, Sumikage L-5H, trademark, a product of Sumitomo Chemical Co., Ltd.). The binders mentioned above may be used in combination of two or more. In particular, it is preferable to use gelatin in combination of some of the above binders. As for the gelatin, lime-treated gelatin, acid-treated gelatin or decalcified gelatin with reduced content of calcium may be appropriately selected depending on the intended purpose. Furthermore, it is preferred that these gelatins are used in combinations.

In the present invention, the weight of the binder used for the coating is preferably not more than 30 g/m², more preferably 1 g/m² to 20 g/m², and particularly preferably 2 g/m² to 15 g/m².

Tetravalent couplers and divalent couplers can both be used in the present invention. Their non-diffusing groups can form a polymer chain. Specific examples of such couplers are described in detail in T. H. James "The Theory of the Photographic Process", fourth edition, pages 2911 to 334 and 354 to 351 and in JP-A Nos. 58-123,533, 58-149,046, 58-149,047, 59-111,148, 59- 124,399, 59-174,835, 59-231,539, 59-231,540, 60-2,950, 60-2,951, 60-14,242, 60- 23,474, 60-66,249, 8-110,608, 8-146,552 and 8-146,578.

In addition, the following couplers are preferably used in the present invention.

Yellow couplers: couplers represented by the formulas (I) and (II) described in EP-A-502424, the couplers represented by the formulas (1) and (2) described in EP-A-513496, the couplers represented by the formula (1) in claim 1 of Japanese Patent Application No. 4-134,523, the couplers represented by the formula D in column 1, lines 45 to 55 of US Patent No. 5,066,576, the coupler represented by the formula D in paragraph [0008] of JP-A No. 4-274,425, the coupler described in claim 1 (on page 40) of EP-A1-498,381, the coupler represented by formula (Y) on page 4 of EP-A1-447,969, and the couplers represented by formulas (I) to (IV) in column 7, lines 36 and 58 of US Patent No. 4,476,219.

Magenta coupler: Couplers described in JP-A Nos. 3-39,737, 6-43,611, 5-204,106 and 4- 3,626.

Cyan coupler: Couplers described in JP-A Nos. 4-204,843, 4-43,345 and Japanese Patent Application No. 4-23,633.

Polymer couplers: Couplers described in JP-A No. 2-43,345.

Examples of preferred couplers which allow color-developing dyes to exhibit a sufficient diffusion property include those described in U.S. Patent No. 4,366,237, GB-2,125,570, EP-096570 and DE-3-,234,533.

Examples of the couplers which can be used in the present invention may include those described in the aforementioned literature concerning the color developing agents as well as those described in the references of these literatures. Typical examples of the couplers are shown below. tetravalent couplers divalent couplers

Furthermore, the light-sensitive material used in the present invention may contain a functional coupler, for example, a coupler designed to correct the unnecessary absorption of dyes, such as the yellow-colored cyan couplers described in EP-A1-456,257, the yellow-colored magenta couplers described in EP, supra, the magenta-colored cyan coupler described in U.S. Patent No. 4,833,069, and the colorless marking couplers represented by (2) of U.S. Patent No. 4,837,136 and formula (A) in claim 1 of WO 92/11575 (particularly the compounds on pages 36 to 45) as examples thereof.

Examples of the compounds (including couplers) which react with the oxidation product of a developing agent to release photographically important compound residues include the following compounds: development inhibitor-releasing compounds such as those represented by formulas (I) to (IV) in EP-A1-378,236 (page 11), compounds represented by formula (I) in EP-A2-436,938 (page 7), compounds represented by formula (I) in JP-A No. 53-307248, compounds represented by formulas (I), (II) and (III) in EP-A2-440,195 (pages 5-6), compounds (ligand-releasing compound) represented by formula (I) in claim 1 of JP-A No. 6-59411 and compounds represented LIG-X in claim 1 of U.S. Patent No. 4,555,478.

In the present invention, it is preferred to use a coupler or other compounds which react with the oxidation product of a developing agent to release a photographically important compound.

In the present invention, the amount of the coupler to be introduced is preferably 1/1000 to 1 mol, particularly preferably 1/500 to 1/5 mol per mol of the silver halide.

The light-sensitive material used in the present invention preferably contains a developing agent which, in the course of silver development, produces an oxide capable of coupling with the aforementioned coupler to form a dye.

Examples of the compounds of a contained developing agent for forming a dye may include: an aromatic primary amine developing agent or a precursor thereof described in U.S. Patent No. 803,783, 3,42,597, 3,719,492, 4,060,418, British Patent No. 1,069,061, German Patent No. 3,159,758, JP-B No. 58-14,671, 58-14,672, JP-A No. 57-76,543 and 59-81,643. Examples of the compounds of a hydrazine type developing agent are described in U.S. Patent No. 4,481,268, EP-545,491, 565,165, JP-A 7-219,180, 8-286,340, 8-227,131 and 8-234,388. Further, examples of the compounds of the sulfonamide phenol type developing agents are described in U.S. Patent No. 4,021,240, JP-A Nos. 8-110,608, 8-146,552, 8-122,994, 9-15806 and 9-146,248.

p-Phenylenediamine (which is a developing agent) and a phenol coupler or an active methylene coupler can be used in combination, as described in U.S. Patent No. 3,531,256. Similarly, p-aminophenol (which is a developing agent) and an active methylene coupler can be used in combination, as described in U.S. Patent No. 3,761,270.

Furthermore, a combined use of a sulfonamide phenol and a tetravalent coupler, which is described in U.S. Patent No. 4,021,240 and JP-A No. 60-128,438, is preferred because this combination ensures excellent storage stability when a developing agent is contained in a light-sensitive material.

When a developing agent is included, a precursor of a color-forming developing agent may be used, examples of which include an indoaniline compound described in U.S. Patent No. 3,342,597, a Schiff base type compound described in U.S. Patent No. 3,342,599 and Research Disclosure Nos. 14,850 and 15,159, an aldol compound described in Research Disclosure No. 13,924, a metal salt complex described in U.S. Patent No. 3,719,492, and a urethane compound described in JP-A No. 53-135,628.

In the present invention, it is preferable to use a compound represented by any one of the formulas ID, II D, III D or IV D as a developing agent. Of these compounds, the compounds represented by the formula ID or II D are particularly preferred. These developing agents are described in detail below. Formulas ID Formulas IID Formulas IIID Formulas IVD

wherein each of R₁ to R₄ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylcarbamoyl group, an arylcarbamoyl group, a carbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, or an acyloxy group; R₅ represents an alkyl group, an aryl group, or a heterocyclic group; Z represents a group of atoms forming a (hetero)aromatic ring, and when Z is a benzene ring, the sum of Hammett's constants (σ) of the substituents is preferably not less than 1; R6 represents an alkyl group; X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom; R7 and R8 may be bonded together to form a double bond or a ring. The compounds represented by the formulas I D to IV D each have at least one ballast group having eight or more carbon atoms so that the molecule becomes oil-soluble.

The compounds represented by formula I D are generally called sulfonamide phenols, which are known in this technical field. When used in the present invention, it is preferred that at least one of the substituents R₁ to R₅ has a ballast group with eight or more carbon atoms.

In the above formulas, each of R₁ to R₄ represents a hydrogen atom, a halogen atom (e.g. Cl or Br), an alkyl group (e.g. methyl, ethyl, isopropyl, n-butyl, or t-butyl), an aryl group (e.g. phenyl, tolyl or xylyl), an alkylcarbonamide group (e.g. acetylamino, propionylamino, butyroylamino), an arylcarbonamide group (e.g. benzoylamino), an alkylsulfonamide group (e.g. methanesulfonylamino or ethanesulfonylamino), an arylsulfonamide group (e.g. benzosulfonylamino or toluenesulfonylamino), an alkoxy group (e.g. methoxy, ethoxy or butoxy), an aryloxy group (e.g. phenoxy), an alkylthio group (e.g. methylthio, ethylthio or butylthio), an arylthio group (e.g. phenylthio or tolylthio), an alkylcarbamoyl group (e.g. methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidylcarbamoyl or morpholylcarbamoyl), an arylcarbamoyl group (e.g. phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), a carbamoyl group, an alkylsulfonamoyl group (e.g. methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidylsulfamoyl or morpholylsulfamoyl), an arylsulfamoyl group (e.g. phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), a sulfamoyl group, a cyano group, an alkylsulfonyl group (e.g. methanesulfonyl or ethanesulfonyl), an arylsulfonyl group (e.g. phenylsulfonyl, 4-chlorophenylsulfonyl or p-toluenesulfonyl), an alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl or butoxycarbonyl), an aryloxycarbonyl group (e.g. phenoxycarbonyl), an alkylcarbonyl group (e.g. acetyl, propionyl or butyroyl), an arylcarbonyl group (e.g. benzoyl or alkylbenzoyl), an acyloxy group (e.g. acetyloxy, propionyloxy or butyroyloxy). Of the groups of R₁ to R₄, R₂ and R₄ are preferably hydrogen atoms. A sum of constants (σp) of Hammett's substituents of R₁ to R₄ is preferably not less than 0. R₅ represents an alkyl group (e.g. methyl, ethyl, butyl, octyl, lauryl, cetyl or stearyl), an aryl group (e.g. phenyl, tolyl, xylyl, 4-methoxyphenyl, docecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl), or 4-dodecyloxyphenyl or a heterocyclic group (e.g. pyridyl).

The compounds represented by formula II D are generally called carbamoylhydrazines. The above two groups of compounds are known in this technical field. When used in the present invention, it is preferred that the substituents also have on the ring or on R₅ a ballast group having eight or more carbon atoms.

In the formula II D, Z represents a group of atoms forming a (hetero)aromatic ring. The (hetero)aromatic ring represented by Z should be sufficiently electron attractive to impart silver developing activity to the compound. From this point of view, aromatic rings which form a nitrogen-containing aromatic ring or which are prepared by introducing an electron attractive group into a benzene ring are preferred. Examples of such aromatic rings include a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring and a quinoxaline ring. Examples of the substituents on the benzene ring include an alkylsulfonyl group (e.g., methanesulfonyl or ethanesulfonyl), a halogen atom (e.g. chlorine or bromine), an alkylcarbamoyl group (e.g. methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidinecarbamoyl or morpholinecarbamoyl), an arylcarbamoyl group (e.g. phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl or benzylphenylcarbamoyl), a carbamoyl group, an alkylsulfamoyl group (e.g. methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidylsulfamoyl or morpholylsulfamoyl), an arylsulfamoyl group (e.g. phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), a sulfamoyl group, a cyano group, an alkylsulfonyl group (e.g. methanesulfonyl or ethanesulfonyl), an arylsulfonyl group (e.g. phenylsulfonyl, 4-chlorophenylsulfonyl, or p-toluenesulfonyl), an alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl or butoxycarbonyl), an aryloxycarbonyl group (e.g. phenoxycarbonyl), an alkylcarbonyl group (e.g. acetyl, propionyl or butyroyl) or an arylcarbonyl group (e.g. benzoyl or alkylbenzoyl). Preferably, the sum of the Hammett's constants σ of the substituents described above is not less than 1.

The compounds represented by formula III D are generally called carbamoylhydrazones. The compounds represented by formula IV D are generally called sulfonylhydrazines. These two groups of compounds are known in the art. When used in the present invention, preferably at least one of R5 to R8 has a ballast group having eight or more carbon atoms.

In the above formulas, R₆ represents an alkyl group (e.g., methyl or ethyl). X represents an oxygen atom, a sulfur atom, a selenium atom, or an alkyl-substituted or aryl-substituted tertiary nitrogen atom, with the alkyl-substituted tertiary nitrogen atom being particularly preferred. Each of R₇ and R₈ represents a hydrogen atom or a substituent (such as one listed above as a substituent for the benzene ring of Z), and R₇ and R₈ may be joined together so as to form a double bond or a ring.

Of the compounds of formulas I D to IV D, formulas I D and II D are particularly preferred from the point of view of superior storage stability.

In the above compounds, the substituents R₁ to R₈ may each have a substituent, examples of which include those given for the substituents of the benzene ring Z described above.

Specific examples of the compounds represented by formulas ID to IV D are given below, but the developing agents which can be used in the present invention are not limited only to these examples.

A developing agent of the following formula is also preferred.

The compounds described above can generally be synthesized using known methods. Simple synthetic routes are presented below. Synthesis of developing agent D-2 Synthesis of developing agent D-62 Synthesis of developing agent D-77

In the case where a non-diffusing developing agent is used, an electron transport agent and/or a precursor thereof may optionally be used to accelerate electron transfer between the non-diffusing developing agent and the silver halide to be developed. The use of the electron transport agents and precursors thereof described in U.S. Patent No. 5,139,919 and EP-A 418,743 are particularly preferred in the present invention. The use of a method for introducing the electron transport agent and/or precursor thereof into a layer in a stable manner described in JP-A Nos. 2-230,143 and 2-235,044 is also preferred in the present invention.

The electron transport agent and the precursor thereof can be selected from the above-mentioned developing agents and their precursors. The mobility of the electron transport agent or a precursor thereof is preferably greater than that of a non-diffusing developing agent (electron donor). Particularly suitable electron transport agents are 1-phenyl-3-pyrazolidones or aminophenols.

In addition, the electron donor precursors described in JP-A No. 3-160,443 are preferred for use in the light-sensitive material of the present invention.

For such purposes as preventing color mixing, improving color reproduction, a reducing agent may be used in an intermediate layer or in a protective layer. The reducing agents described in EP-A Nos. 524,649 and 357,040 and in JP-A Nos. 4-249,245, 2-46,450 and 63-186,240 are particularly preferred for use in the present invention. Also usable are development inhibitor-releasing reducers described in JP-B No. 3-63,733, JP-A Nos. 1-150,135, 2-46,450, 2-64,634, and 3-43,735 and in EP-A No. 451,833.

Furthermore, a precursor of a developing agent which does not have reducing properties per se but which provides reducing properties under the influence of a nucleophilic reagent or heat in the course of development can be used in the light-sensitive material of the present invention.

Furthermore, the following reducing agents can be introduced into the photosensitive material.

Examples of the reducing agents which can be used in the present invention include reducing agents and precursors thereof as described in U.S. Patent No. 4,500,626 (columns 49 to 50), U.S. Patent Nos. 4,829,272, 4,330,617, 4,590,152, 5,017,454 and 5,139,919, JP-A No. 60-140,335 (pages 17 to 18), 57-40,245, 56-138,736, 59-178,458, 59-53,831, 59-182,449, 59-182,455, 60-119,555, 60-128,436, 60-128,439, 60-198,540, 60-181,742, 61-259,252, 62-244,044, 62-131,253, 62-131,256, 64-13,546 (pages 40 to 57), 1-120,553, and EP-A2-220,746 (pages 78 to 96).

Furthermore, combinations of different reducing agents, as described in US Patent No. 3,039,869, can also be used.

A developing agent or a reducing agent may be incorporated into a processing sheet, as hereinafter referred to, or into a light-sensitive material.

In the present invention, the total amounts of the developing agent and the reducing agent are 0.1 to 20 mol, preferably 0.01 to 10 mol, per mol of silver.

In the present invention, tetravalent couplers or divalent couplers can be appropriately selected according to the kind of the developing agent. Appropriate selection of the couplers prevents the formation of dull colors attributed to interlayer transition of the oxides of the developing agent. Specific examples of both kinds of couplers, i.e., tetravalent couplers and divalent couplers, are described in detail in "The Theory of the Photographic Process", fourth edition, edited by T. H. James, pages 291 to 334, 354 to 361, JP-A No. 58-12,353, 58-149; 046, 58-149,047, 59-11,114, 59-124,399, 59-174,835, 59-231,539, 59-231,540, 60-2,951, 60-14,242, 60-23,474,60-66,249, and in the other patents and literature cited above.

Hydrophobic additives such as couplers and developing agents for forming a color tone can be introduced into the layers of a light-sensitive material by known methods described in U.S. Patent No. 2,322,027. In this case, an organic solvent having a high boiling point described in, for example, U.S. Patent Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476, 4,599,296, or JP-B No. 3-62,256 can be used, if necessary, in combination with an organic solvent having a low boiling point in the range of 50° to 160°C. These dye-providing compounds and organic solvents having a high boiling point can be used in combination of two or more kinds.

The amount of the organic solvent having a high boiling point is not more than 10 g, preferably not more than 5 g, and particularly preferably in the range of 1 g to 0.1 g based on 1 g of the hydrophobic additive; or not more than 1 cc, preferably not more than 0.5 cc, particularly preferably not more than 0.3 cc based on 1 g of the binder.

A dispersion method using a polymer as described in JP-B No. 51-39,853 and JP-A No. 51-59,943 and a method in which a hydrophobic additive converted into a fine grain dispersion is added to a photosensitive material as described in JP-A No. 62-30,242 can be used.

In addition to the above methods, in the case where the hydrophobic additive is a compound that is substantially insoluble in water, the hydrophobic compound can be converted into a dispersion of fine grains and incorporated into a binder.

When a hydrophobic compound is dispersed to form a hydrophilic colloidal dispersion, a variety of surfactants can be used. For example, the surfactants described in JP-A No. 59-157,636, pages 37 to 38 and in the aforementioned Research Disclosure can be used. In addition, a phosphoric ester type surfactant described in JP-A Nos. 7-56,267 and 7-228,589 and in the German Laid-Open Patent Application No. 1,932,299A can also be used in the light-sensitive material of the present invention.

The light-sensitive material used in the present invention may contain a compound which activates development and stabilizes the image. Preferred examples of these compounds are described in U.S. Patent No. 4,500,626, columns 51 to 52.

The light-sensitive material used in the present invention may contain at least three kinds of light-sensitive layers having different spectral sensitivities and different color tones. Each of the layers may be divided into a plurality of silver halide emulsion layers having substantially the same color sensitivity but having different light sensitivities. Each of the above three kinds of layers is preferably sensitive to blue light, green light or red light. The arrangement is generally in the following order: red-sensitive layer, green-sensitive layer and blue-sensitive layer starting from the support. Other arrangements may be employed according to the purpose. For example, an arrangement described in JP-A No. 7-152,129 may be employed. Silver halides, dye-donating couplers and color developing agents suitable for use in the present invention may be contained in the same layer or may be added to different layers as long as they can react. For example, if the silver halide emulsion layers are used, the silver halide emulsion layers may be used in the same layer or may be added to different layers. For example, if a layer containing a color developing agent and a layer containing a silver halide are arranged separately from each other, the storage stability of the light-sensitive material can be increased.

The relationship between the spectral sensitivity of each layer and the hue of a coupler is arbitrary. If a light-sensitive material is constructed to contain a cyan coupler in a red-sensitive layer, a magenta coupler in a green-sensitive layer, and a yellow coupler in a blue-sensitive layer, ordinary color papers can be used for direct exposure.

Unlike the yellow filter layer, magenta filter layer and cyan filter layer mentioned above, a variety of non-light-sensitive layers, such as a protective layer, an undercoat layer or an intermediate layer may be formed between the silver halide emulsion layers of the light-sensitive material, on the uppermost emulsion layer or on the lowermost emulsion layer. Furthermore, a plurality of additional layers such as a backing layer may be formed on the other side of the support. In particular, it is possible to form various layers comprising the above-mentioned make-up layer, an undercoat layer described in U.S. Patent No. 5,051,335, an intermediate layer containing a solid pigment described in JP-A Nos. 1-167,838 and 61-20,943, an intermediate layer containing a reducing agent or a DIR compound described in JP-A Nos. 1-120,553, 5-34,884 and 2-64,634, an intermediate layer containing an electron transport layer described in U.S. Patent Nos. 5,017,454 and 5,139,919 and in JP-A No. 2-235,044, and a protective layer containing a reducing agent described in JP-A No. 4-249,245, as well as a combination of two or more of these layers.

A dye used in a yellow filter layer or in the antihalation layer is preferably a dye which loses color or which is eliminated at the time of development so that it has no influence on the density of an image after the process.

The dye present in the yellow filter layer or in the antihalation layer loses its color or is eliminated at the time of development when the amount of the dye remaining after processing is less than one-third, preferably less than one-tenth, of the amount of the dye present before processing. This can be achieved by a phenomenon in which the dye component is leached out of the light-sensitive material or transferred into the processing material at the time of development, or by a phenomenon in which the dye component is subjected to a reaction and becomes a colorless compound at the time of development.

The photosensitive material used in the present invention is preferably hardened with a hardener.

Examples of the curing agents include those described in U.S. Patent No. 4,678,739, column 40 and 4,791,042 and JP-A Nos. 59-116,655, 62-245,261, 61-18,942 and 4- 218,044. Specifically, examples of these curing agents include an aldehyde (e.g., formaldehyde), an aziridine, an epoxy resin, a vinyl sulfone (e.g., N,N'-ethylenebis(vinylsulfonylacetamide)ethane), an N-methylol compound (e.g., dimethylolurea), boric acid, metaboric acid, and a polymer compound (e.g., a compound described in JP-A No. 62-234,157).

The hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g per gram of a hydrophilic binder.

The light-sensitive material may contain an antifoggant or a photographic stabilizer, as well as a precursor thereof, examples of which include the compounds described in the aforementioned Research Disclosure, U.S. Patent Nos. 5,089,378, 4,500,627 and 4,614,702, in JP-A No. 64-13,564, pages 7 to 9, pages 57 to 71 and pages 81 to 97, U.S. Patent Nos. 4,775,610, 4,626,500, and 4,983,494, JP-A Nos. 62-174,747, 62-239,148, 1-150,135, 2-1110,557, 2-178,650 and in RD 17,643. (1978) Pages 24 to 25.

The amount of these compounds is preferably in the range of 5 x 10⁻⁶ to 1 x 10⁻¹ mol, more preferably 1 x 10⁻⁵ to 1 x 10⁻² mol, per mol of silver.

After the photosensitive material of the present invention is subjected to image forming exposure, images are formed by first bonding the photosensitive material after exposure to a processing material having a carrier and a base and/or a base precursor thereon so that the surface of the photosensitive layer and the surface of the processing layer of the processing material are bonded together, and then subjecting it to heat development. It is preferable that water in an amount of 10% to 100% necessary for maximum swelling of the entirety of the coating film constituting the photosensitive material and the processing material is supplied to the photosensitive material or the processing material during heat development or after the two materials are bonded together and heated for color formation and development. However, the present invention is not limited to such a manner. Furthermore, a developing agent may preferably be incorporated in the photosensitive material. Material or the processing material can be installed according to the requirements. Again, the present invention is not limited in this way.

The light-sensitive material used in the present invention can be processed under conditions in which reacted silver halide remains unfixed. A color image is formed on the light-sensitive material where the silver halide remains. That is, in the case where a light-sensitive material is used while residual silver halide remains thereon, the present light-sensitive material containing a high AgCl tabular grain emulsion having (100) or (111) major faces provides images having excellent sharpness as compared with when other types of silver halides are used, and when the dye used in the present invention having a specific structure is used in combination, even better sharpness can be achieved.

The present invention has been made in an attempt to achieve excellent graininess and exposure size as well as improved sharpness when the aforementioned heat development is carried out and further to reduce the load given to the environment which otherwise occurs by the solution development. However, the present invention can also be subjected to an activation process using an alkaline processing solution or a process in which images are developed by using a processing solution containing a developing agent and a base.

A thermal process of a photosensitive material is well known in the art. For example, a heat-sensitive material for heat development and a heat development process are described in "Shashinkogaku no kiso (Fundamentals of Photographic Engineering)", pages 553-555, Corona Co., Ltd. (1970), "Eiszojoho (Image Information)" (April 1978), page 40, "Nablett's Handbook of Photography and Reprography" 7th edition (Vna Nostrand and Reinhold Company), page to page 33, US Patent Nos. 3,152,904, 3,301,678, 3,392,020 and 3,457,075, UK Patent Nos. 1,131,108 and 1,167,777 and Research Disclosure (June 1978) pages 9-15 (RD-17,029).

The term "activation process" refers to a development process in which a light-sensitive material containing a developing agent is treated with a processing solution which does not contain a developing agent. The special feature of the activation process is that the processing solution for the process does not contain a color developing agent which is contained in a conventional developing solution. The processing solution for the activation process may contain other components such as an alkali or an auxiliary developing agent. Examples of the activation processes are described in the literature, such as in EP-A Nos. 545,491A1 and 565,165A1.

Methods for developing a light-sensitive material using a processing solution containing a developing agent and a base are described in RD No. 17,643, pages 28-29, 18,716, page 651, left column to right column and 307,105, pages 880-881.

Details of the processing material and the processing method used in the heat development method in the present invention are described below.

The light-sensitive material used in the present invention preferably contains a base or a base precursor in order to accelerate the development of the silver and the dye which form the reaction. Examples of the base precursor include a salt of an organic acid and a base capable of decarboxylation by heat and a compound capable of releasing an amine by an intramolecular nucleophilic substitution reaction of a Lossen rearrangement or a Beckmann rearrangement. Examples of these compounds are described in U.S. Patent Nos. 4,514,493 and 4,657,848 as well as in "Know Technologies" No. 5 (issued on March 22, 1991, AZTEC Co., Ltd.), pages 55-86. In addition, in the present invention, a base-generating method is also suitable in which a combination of a readily water-soluble basic metal compound and a compound which can react with the metal contained in the aforementioned basic metal compound is prepared using water as a means for forming a complex compound (hereinafter referred to as a complex formation compound) as described in EP-A No. 210,660 and US Patent No. 4,740,445.

The amount of the base or base precursor used in the present invention is in the range of 0.1 to 20 g/m², preferably 1 to 10 g/m².

The photosensitive material used in the present invention may contain a thermal solvent so as to accelerate heat development. Examples of the thermal solvents include polar organic compounds described in U.S. Patent Nos. 3,347,675 and 3,667,959. Examples of such compounds include amide derivatives (e.g., benzamide), urea derivatives (e.g., methylurea and ethyleneurea), sulfonamide derivatives (e.g., the compounds described in JP-B Nos. 1-40,974 and 4-13,701), polyol compounds (e.g., sorbitols), and polyethylene glycol.

If the thermal solvent is insoluble in water, the thermal solvent is preferably used as a solid dispersion. Depending on the purpose, the thermal solvent may be contained in a photosensitive layer and a non-photosensitive layer.

The temperature of the heat development process is approximately 50ºC to 250ºC, preferably 60ºC to 150ºC.

The amount of thermal solvent is in the range of 10 to 500 wt%, preferably 20 to 300 wt%, based on the weight of the binder present in the layer to which the thermal solvent is to be added.

In order to add a base necessary for the heat development process to the photosensitive material of the present invention, a processing material having a processing layer containing a base or a base precursor is used. The processing material may have other functions, for example, a function of excluding air at the time of heat development, a function of preventing evaporation of the components of the photosensitive material material, a function for supplying a material other than the base to the photosensitive material, and a function for removing a component of the photosensitive material which becomes unnecessary after the development process (e.g., YF dye or AH dye) or an unnecessary component which is formed during the development process. The carrier and the binder for the processing material may be the same as those for the photosensitive material.

The processing material may contain a mordant to remove the dye, as mentioned above or for other purposes. The mordant may be one known in the field of photography, and examples include the mordants described in U.S. Patent No. 4,500,626, columns 58-59, and in JP-A No. 61-88,256, pages 32-41, 62-244,043 and 62-244,036. Furthermore, the processing material may contain a polymeric dye acceptor compound described in U.S. Patent No. 4,463,079, or the thermal solvent mentioned above.

When the processing material is subjected to heat development, a small amount of water is used for the purposes of accelerating development, accelerating transfer of the processing material or accelerating diffusion of unnecessary substances, as described in U.S. Patent Nos. 4,704,245 and 4,470,445 and JP-A No. 61-238,056. Water may optionally contain compounds such as an inorganic salt of an alkali metal, an organic base, a solvent having a low boiling point, a surfactant, an antifogging agent, a compound which forms a complex with a readily water-soluble metal salt, an antimolding agent and an antibacterial agent.

The water is not particularly limited, and examples of the water include distilled water, tap water, spring water, and mineral water. In the heat developing device used in the photosensitive material of the present invention and the processing material, the waste water may be discharged without being reused or may be recycled for repeated use. When recycled water is used, the used water collects the components leached out of the materials by the repeated use. Furthermore, the device and the water may described in JP-A Nos. 63-144,354, 63-144,355, 62-38,460 and 3-210,555 can be used in the present invention.

Water can be applied to the photosensitive material, the processing material, or both.

The amount of water added is in the range of 1/10 to 1 time the amount required for the maximum swelling of the entire coating (excluding the backing layer) constituting the photosensitive material and the processing material.

Water may be added to the photosensitive material or the processing material in such a manner that the material is immersed in water and then taken out to remove the water using a squeegee roller. Preferably, a predetermined amount of water is applied to the photosensitive material or the processing material during a single coating operation. Particularly preferably, a special water application device is used to apply the water in the form of a jet, the device comprising a nozzle and an actuator, the nozzle having a plurality of nozzle holes for spouting the water, which are arranged at certain intervals in a straight line along a direction crossing the feeding direction of the photosensitive material or the processing material, and the actuator directs the nozzle toward the photosensitive material or the processing material on the feeding path.

Preferred examples of the methods for supplying water to the two materials include the methods described in JP-A No. 62-253,159, page 5 and 63-85,544. Furthermore, water contained in microcapsules or in the form of hydrates may be previously introduced into the photosensitive material or the processing material or both.

The temperature of the water to be supplied falls within the range of 30 to 60ºC as described in JP-A No. 63-85,544.

When the light-sensitive material is heat-developed in the presence of a small amount of water, it is effective for generating a base as described in EP-A No. 210660 and U.S. Patent No. 4,740,445, wherein a combination of a readily water-soluble basic metal compound and a compound which forms a complex through the mediation of water and a metal ion which forms the base metal (the compound is referred to as a complex-forming compound). In this case, it is desirable to introduce the hardly water-soluble basic metal compound into the light-sensitive material and to introduce the complex-forming compound into the processing material from the viewpoint of the storability of the starting materials.

Examples of the heating method in the development process include a method in which the photosensitive material is brought into contact with a heated block or plate, a method in which the photosensitive material is brought into contact with such an object as a hot plate, a hot presser, a hot roller, a hot drum, a halogen lamp heating device, and an infrared or far infrared lamp heating device, and a method in which the photosensitive material is passed through a hot atmosphere.

As for the method of arranging the photosensitive material and the processing material face each other so that the photosensitive layer and the processing layer face each other, the methods described in JP-A Nos. 62-253,159 and 61-147,244, page 27 can be used. Preferably, the material is heated to 70 to 100°C.

For the purpose of processing the photosensitive material and the processing material used in the present invention, any known heat development device can be used. Preferred examples of the device include the device described in JP-A Nos. 59-75,247, 59-177,547, 59-181,353 and 60-18,951, Japanese Utility Model Application Laid-Open (JP-U) No. 62-25,944 and Japanese Patent Application Nos. 4-277,517, 4-243,072, 4,244,693, 6-164,421 and 6-164,422.

In addition, commercially available devices such as "Pictrostat" 100, 200, 300, 330 and 50 and "Pictrography" 3000 and 2000 manufactured by Fuji Photo Film Co., Ltd. can be used in the present invention.

The photosensitive material and/or the processing material used in the present invention may have an electroconductive heat generating layer as a heating means for heat development. For example, a heat generating layer described in JP-A No. 61-145,544 may be used.

The photosensitive material which can be used in the present invention may contain a silver oxidizing agent to remove developed silver contained in the photosensitive layer simultaneously with development and to serve as a bleaching agent for the processing material, thus inducing these reactions during the development process.

Alternatively, developed silver may be removed by applying a second material containing a silver oxidizing agent to the photosensitive material after completion of development of the images produced.

However, in order to simplify processing, it is preferred that the developed silver is not decolourised during development.

As for the decolorizing agent that can be used in the processing material, conventionally used silver bleaching agents can be arbitrarily used. Examples of such silver bleaching agents are described in U.S. Patent Nos. 1,315,464 and 1,946,640 and in "Photographic Chemistry," Vol. 2, Chapter 30, Foundation Press, London, England. These decolorizing agents effectively oxidize a silver image to make it soluble. Examples of suitable silver decolorizing agents include an alkali metal salt of dichromic acid and an alkali metal ferricyanide.

Preferred decolorizing agents are water-soluble compounds, examples of which include ninhydrin, indandione, hexaketocyclohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid and 2,5-dinitrobenzoic acid. The decolorizing agents contain also an organic complex of a metal such as a ferric salt of cyclohexyldialkylaminetetraacetic acid, a ferric salt of ethylenediaminetetraacetic acid and a ferric salt of citric acid. Materials of binders, carriers and other additives which can be used to prepare the second processing material may be the same as those described for preparing the previously described processing material (first processing material) for developing the photosensitive material.

The amount of the decolorizing agent which can be added should be determined according to the amount of silver contained in the photosensitive material to be bonded, and is in the range of 0.01 to 10 mol, preferably 0.1 to 3 mol, particularly preferably 0.1 to 2 mol, per mol of the silver supported on the unit area of the photosensitive material.

Both the first processing material and the second processing material may have at least a single polymerizable timing layer. The polymerizable timing layer may temporarily retard the decolorization reaction during the period until the desired reaction among the silver halides, a dye-forming compound or a developing agent is substantially completed.

The timing layer may comprise gelatin, polyvinyl alcohol or polyvinyl acetate. This layer may be a boundary timing layer as described in U.S. Patent Nos. 4,056,394, 4,061,496 and 4,229,516.

When the timing layer is provided by the coating, the film thickness of the timing layer is in the range of 5 to 50 µm, preferably 10 to 10 to 30 µm.

In the present invention, in order to bleach the photosensitive material after it has been developed using the second processing material, a specific amount of water (0.1 to 1 times the amount required to cause the maximum swelling of all of the coated layers except the backing layer on the photosensitive material and the processing materials) is applied to the photosensitive material or the second processing material, and then the photosensitive material and the second processing material are so that the photosensitive layer and the processing layer face each other and then heat (40ºC-100ºC) is applied for 5 to 60 seconds.

Regarding the amount of water, the kind of water, the method of supplying the water and the method of arranging the photosensitive material and the second processing material in opposition to each other, the same conditions as those in the case of the first processing material can be employed.

In particular, the bleaching films described in JP-A No. 59-136,733, in US Patent No. 4,124,398 and in JP-A No. 55-28,098 can be used in the present invention.

After being subjected to heat development, the light-sensitive material of the present invention is used as a negative original with unreacted silver halide remaining unfixed, whereby the unreacted silver halide substantially remains on the light-sensitive material, so as to form images on, for example, paper.

In the present invention, the expression "leaving unreacted silver halide unfixed" is intended to mean that no fixing step was carried out as an additional step after heat development.

In the present invention, the expression "the unreacted silver halide substantially remains" is intended to mean that not less than 50 mol%, preferably not less than 70 mol%, particularly preferably not less than 80 mol% of the unreacted silver halide remains.

In the present invention, it is preferable that the processing period from the time when the layer surfaces of the processing sheet and the photosensitive material are brought into contact with each other in the presence of water to the time when the two are separated from each other is within 30 seconds.

In order to improve coatability, release or lubricity, ensure antistatic performance and accelerate development reaction, a variety of surfactants can be incorporated into the photosensitive material. Examples of the surfactants include those described in "Known Technologies" No. 5 (issued on March 22, 1991, AZTEC Co., Ltd.), pages 136-138 and JP-A Nos. 62-173,463 and 62-185,457.

For purposes such as preventing excessive lubricity, preventing electrostatic charge and improving release, organic fluorine-containing compounds may be added to the photosensitive material. Typical examples of the organic fluorine-containing compounds include fluorine-containing patches, surfactants and hydrophobic fluorine-containing compounds such as an oily fluorine-containing compound such as fluorocarbon oil and a solid fluorine-containing resin such as tetrafluoroethylene described in JP-B No. 57-9053, column 8-17, in JP-A No. 61-20,944 and in 62-135,826.

Preferably, the photosensitive material has a certain degree of lubricity. For this purpose, it is preferred that a lubricant is present in both the photosensitive layer and the backing layer. A preferred degree of lubricity is indicated by a coefficient of dynamic friction in the range between 0.01 and 0.25 inclusive, which is determined in a test comprising sliding the photosensitive material at a speed of 60 cm/min over stainless steel balls with a diameter of 5 mm (25ºC, 60% room humidity). In this test, a value close to the same degree is obtained even if the stainless steel balls are replaced by a photosensitive layer.

Examples of suitable surfactants include polyorganosiloxanes, higher aliphatic acid amides, metallic salts of higher fatty acids, and esters of higher fatty acids and higher alcohols. Examples of the polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, polystyrenemethylsiloxane, and polymethylphenylsiloxane. The layer to which the surfactant is added is preferably the outermost emulsion layer or the backing layer. Polydimethylsiloxane and an ester having a long alkyl chain are particularly preferred.

It is preferable to use an antistatic agent in the present invention. Polymers containing carboxylic acid, a carboxylic acid salt or a sulfonic acid salt, cationic polymers and ionic surfactants can be used as antistatic agents.

The most preferable antistatic agents are grains of at least one kind of crystalline metal oxide having grain sizes in the range of 0.001 to 1.0 µm selected from the group consisting of ZnO, TiO₂, SnO₂, AbO₃, In₂O₃, SiO₂, MgO, BaO, MoO₃ and V₂O₅ and having a volume resistivity of 10⁷ Ω·cm or less, preferably 10⁵ Ω·cm or less, or grains of a complex oxide of these, for example, a complex of an element such as Sb, P, B, In, S, Si, C and the aforementioned metal oxide. Metal oxides in the form of sols and fine particles of a complex oxide of such metal oxides are also preferable. The amount of an antistatic agent contained in the photosensitive material is preferably in the range of 5 to 500 mg/m², more preferably in the range of 10 to 350 mg/m². The ratio of an electroconductive crystalline oxide or a complex oxide thereof to a binder is preferably in the range of 1/300 to 100/1, more preferably 1/100 to 100/5.

Constituent layers (including a back layer) of the photosensitive material or the processing material described below may contain a polymer latex in order to improve layer properties such as dimensional stability, prevention of curling, prevention of sticking, prevention of film cracking, and prevention of pressure-induced sensitization or desensitization. Any polymer latex described in JP-A Nos. 62-425,258, 62-136,648 and 62-110,066 can be used in the present invention. In particular, the use of a polymer latex having a low glass transition point (40°C or less) in a processing layer prevents the generation of cracks in the layer, whereas the use of a polylatex having a high glass transition point in the back layer prevents curling.

Preferably, the photosensitive material used in the present invention contains a matting agent. Although the matting agent may be added to either the photosensitive layer or the backing layer, it is particularly It is preferable that the matting agent is added to the outermost layer on the emulsion side. Although the matting agent may be soluble or insoluble during processing, it is preferable to use a combination of a soluble matting agent and an insoluble matting agent in the present invention. An example of such a combination of matting agents includes grains of polymethyl methacrylate, poly(methyl methacrylate/methacrylic acid) (in a molar ratio of 9/1 or 5/5) and polystyrene. Preferably, the matting agent has grain diameters in the range of 0.8 to 10 µm. Furthermore, the matting agent preferably has a narrow distribution range of grain diameter. It is preferable that 90% or more of the total number of grains have a diameter falling in the range of 0.9 to 1.1 times the average grain diameter. Furthermore, in order to enhance the matting effect, it is preferable to use fine grains having a grain diameter of 0.8 µm or less together with the matting agent having the above-mentioned grain diameter. Examples of fine grains include grains of polymethyl methacrylate (0.1 µm), grains of poly(methyl methacrylate/methacrylic acid) (in a molar ratio of 9/1, 0.3 µm), grains of polystyrene (0.25 µm) and grains of colloidal silica (0.03 µm).

Specific examples of the matting agent are described in JP-A No. 61-88,256, page 29. Other examples of matting agents are benzoguanamine resin beads, polycarbonate beads and AS resin beads described in JP-A No. 63-274,944 and 63-274,952. Furthermore, the compounds described in the aforementioned Research Disclosure can be used as the matting agent.

In the present invention, a support for the photosensitive material may be transparent and capable of withstanding the processing temperature. In general, examples of the support are paper or a synthetic polymer (layer) as described in "Shashinkogaku no kiso - Gin'en Shashin Hen (Fundamentals of Photographic Engineering - Silver Salt Photography Section)" pages 223-240, published by the Photographic Society of Japan, Corona Co., Ltd. in 1979. Specific examples of the support include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and cellulose (e.g., triacetyl cellulose).

Other supports which can be used in the present invention include those described in JP-A No. 62-253,159, pages 29-31, 1-161,236, pages 14-17, 63-316,848, 2-22,651 and 3-56,955 and U.S. Patent No. 5,001,033.

In the case where higher levels of resistance to heat and curl are required, the supports described in the following publications can be preferably used. JP-A Nos. 6-41,281, 6-43,581, 6-51,426, 6-51,437, 6-51,442, 6-82,961, 6-82960, 6-123,937, 6-82,959, 6-67,346, 6-118,561, 6-266,050, 6-202,277, 6-175,282, 6-118,561, 7,219,129 and 7-219,144.

Furthermore, a carrier is preferred which mainly consists of a styrene-based polymer having a syndiotactic structure.

In order to bond the photographic layer to the support, it is preferable that the support is surface-treated. Examples of the surface treatment include a chemical method, a mechanical method, a corona discharge method, a flame method, an ultraviolet ray method, a high frequency wave method, a glow discharge method, an activated plasma method, a laser method, a mixed acid method and an ozone oxidation method. Among these surface methods, an ultraviolet ray method, a flame method, a corona discharge method and a glow discharge method are particularly preferable.

An undercoat layer may comprise a single layer or two or more layers. A typical example of the binder for the undercoat layer may be a copolymer consisting of a monomer selected from the group consisting of vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride. Other examples of the binder may be polyethyleneimine, an epoxy resin-grafted gelatin, nitrocellulose and gelatin. Examples of the compound which swells the support include resorcinol and p-chlorophenol. The undercoat layer may contain a gelatin hardener such as chromates (e.g., chromalum), aldehydes (e.g., formaldehyde and glutaraldehyde), isocyanates, active halogen compounds (e.g., 2,4-dichloro-6-hydroxys-triazine), an epichlorohydrin resin and active vinylsulfone compounds. Further, the undercoat layer may contain SiO₂, TiO₂, grains of an inorganic material or grains of a copolymer or polymethyl methacrylate (0.01 to 10 µm) as a matting agent.

It is preferable to record the photographic information using a support provided with a magnetic recording layer described in JP-A Nos. 4-124,645, 5-40,321, 6-35,092, 5-58,221 and 6-317,875.

The magnetic recording layer is formed by applying an aqueous or organic solvent-based coating solution comprising a binder and magnetic grains dispersed therein to a support.

Examples of suitable magnetic grains include ferromagnetic iron oxide such as γ-Fe₂O₃, Co-coated γ-Fe₂O₃, Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metals, ferromagnetic alloys, hexagonal B ferrite, Sr ferrite, Pb ferrite and Ca ferrite. A Co-coated ferromagnetic iron oxide such as Co-coated γ-Fe₂O₃ is preferred. The magnetic grains may have the shape of needles, rice grains, spheres, cubes or plates. The specific surface area in SBET is preferably 20 m²/g or more, more preferably 30 m²/g or more. The saturation magnetization (s) of the ferromagnets is preferably in the range of 3.0 x 10⁴ to 3.0 x 10⁵ Å/m, particularly preferably 4.0 x 10⁴ to 2.5 x 10⁵ Å/m. The ferromagnetic grains may be surface-treated with silicon dioxide and/or aluminum dioxide or with an organic substance. Furthermore, the ferromagnetic grains may be surface-treated with a silane coupling agent or with a titanium coupling agent as described in JP-A No. 6-161,032. Magnetic grains covered with an inorganic or organic substance described in JP-A No. 4-259,911 and 5-81,652 may also be used in the present invention. be used.

As described in JP-A No. 4-219,569, the binders which can be used together with the magnetic grains are thermoplastic resins, thermosetting resins, radiation-curing resins, reactive resins, acid, alkali or biodegradable polymers, naturally occurring polymers (e.g., cellulose derivatives and derivatives of saccharides), and mixtures thereof. These resins have a Tg in the range from -40 to 300°C and an average molecular weight in the range of 2,000 to 1,000,000. Preferred examples of the binders include vinyl-based copolymers, cellulose derivatives (e.g., cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butylate, and cellulose tripropionate), acrylic resins, and polyvinyl acetal resins. Cellulose di(tri)acetate is particularly preferred. The binders can be cured using a crosslinking agent such as an epoxy, aziridine, or isocyanate crosslinking agent. Examples of the isocyanate type crosslinking agents include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, a reaction product of one of these isocyanates and polyalcohol (e.g., a reaction product of tolylene diisocyanate (3 mol) and trimethylolpropane (1 mol) and a polyisocyanate prepared by a condensation reaction of these isocyanates), which are described in, for example, JP-A No. 6-59,357.

As described in JP-A No. 6-35,092, the aforementioned magnetic grains are dispersed in a binder, preferably by means of a kneader, a pin mill or an annular mill. The use of these dispersing agents in combination is also preferred. The dispersing agents described in JP-A No. 5-88,283 and other known dispersing agents can be used to disperse the magnetic grains in the binder. The thickness of the magnetic recording layer is in the range of 0.1 to 10 µm, preferably 0.2 to 5 µm, preferably 0.2 to 5 µm, and particularly preferably 0.3 to 3 µm. The ratio of the weight of the magnetic grains to the weight of the binder is preferably in the range of 0.5:100 to 60:100, more preferably 1:100 to 30:100. The amount of the magnetic grains used for coating is in the range of 0.005 to 3 g/m², preferably 0.01 to 2 g/m², and more preferably 0.02 to 0.5 g/m². The transmission density of the magnetic recording layer for yellow is preferably in the range of 0.01 to 0.50, more preferably 0.03 to 0.20, and most preferably 0.04 to 0.15. The magnetic recording layer can be applied to the entire surface or in stripes on the back of a photographic support by coating or printing. In forming the magnetic recording layer, an air knife method, a blade method or an air cutting method, pressing, dipping, reverse roll coating, transfer roll coating, pressure coating, sanding coating, pouring, spraying, Dipping, bar coating or extrusion may be used. The coating solution as described in, for example, JP-A No. 5-341,436 is preferably used.

The magnetic recording layer can also be used for increasing lubricity, controlling curl, preventing electrostatic charge, preventing sticking and polishing the head. Furthermore, other functional layers that perform any of these functions can be formed. The abrasive grains that impart a head grinding function to the magnetic recording layer or other functional layer preferably contain a type of grains having a Mohs hardness of 5 or more and are non-spherical inorganic grains. Examples of these non-spherical inorganic grains include oxides (such as aluminum oxide, chromium oxide, silicon dioxide and titanium dioxide), carbides (such as silicon carbide and titanium carbide); and fine powder of diamond. The surface of the abrasive grains may be treated with a silane coupling agent or with a titanium coupling agent. These grains may be added to the magnetic recording layer. Alternatively, the magnetic recording layer may be coated with a solution coating (e.g., a protective layer and a lubricating layer) containing these grains. As for the binder for the coating, the same binders as those mentioned above can be used, and preferably the same as those listed for the magnetic recording layer. The photosensitive materials having a magnetic recording layer are described in U.S. Patent Nos. 5,336,589, 5,250,404, 5,229,259, and 5,215,874 and EP 466,130.

Polyester supports preferably used in the photosensitive material having the above-described magnetic recording layer are described below. Details of the polyester supports comprising the photosensitive material, processing methods, supports and examples of use are shown in JIII Journal of Technical Disclosure No. 94-6,023 (issued on March 15, 1994, The Japan Institution of Invention and Innovation). The polyester consists of a diol and an aromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and phthalic acid. Examples of the diol include diethylene glycol, triethylene glycol, cyclohexanoldimethanol, bisphenol A and bisphenol. Examples of the polymers consisting of These monomers include homopolymers such as polyethylene terephthalate, polyethylene phthalate and polycyclohexanedimethanol terephthalate. A polyester containing 2,6-naphthalenedicarboxylic acid in an amount of 50 to 100 mol% is preferred, and polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight of the polyester is in the range of about 5,000 to 200,000. The Tg of the polyester is 50°C or more, preferably 90°C or more.

In order to make the polyester support resistant to curling, the polyester support is subjected to a heat treatment in a specific temperature range (preferably not less than 40°C but below Tg, particularly not lower than (Tg - 20)°C but below Tg). The heat treatment may be carried out at a constant temperature within the above range, or it may be carried out while cooling. The duration of the heat treatment is preferably in the range of 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment may be carried out while the support is kept in the form of a roll, or the heat treatment may be carried out while the support is in the form of a net. Electroconductive inorganic particles such as SnO₂ and Sb₂O₅ may be provided on the surface of the support to impart a surface roughness so that the surface property is improved. Furthermore, it is preferable that the support is formed in such a manner that the ends of the roll are slightly raised relative to the other parts so that the transfer of the cut end mark into the roll core is prevented. Although the heat treatment may be carried out after the film formation, after the surface process, after the application of the back layer (e.g., an antistatic agent, lubricant and after the arrangement of an undercoat layer, the heat treatment is preferably carried out after the application of an antistatic agent.

A light stabilizer may be blended into the polyester. In order to prevent easy void formation, a dye or pigment commercially available for use in polyesters under the name "Diaresin" (from Mitsubishi Chemical Industries, Co., Ltd.) or "Kayaset" (from Nihon Kayaku Co., Ltd.) may be blended into the polyester.

A film magazine in which the photosensitive material of the present invention can be enclosed is described below. The main material of the film magazine may be a metal or a synthetic resin.

Preferred examples of the plastic material include polystyrene, polyethylene, polypropylene and polyvinyl ether. The film magazine may contain an antistatic agent, examples of which include carbon black, metal oxide particles, surfactants (nonionic, anionic, cationic and betaine surfactants) and polymers. Examples of the magazines which have been found to be antistatic are described in JP-A No. 1-312,537 and 1-312,538. The resistance of the magazine is preferably 1012 Ω·cm or less under a condition of 25°C and 25% humidity. In general, carbon black or a pigment is introduced into the plastic magazine to impart light protection thereto. The size of the magazine may be 135 size which is currently used (the diameter of the 135 size casing is 25 mm). For use in a small-sized camera, a film magazine with a diameter of 22 mm or less can be used. The housing volume of the magazine is 30 cm³ or less, preferably 25 cm³ or less. The weight of the plastics for a film magazine is preferably in the range of 5 g to 15 g.

A film magazine which feeds the film by rotating a spool can be used for the photosensitive material of the present invention. A film magazine in which the end of the film is fed out from the exit of the film magazine to the outside by rotating the spool axis in the direction of feeding the film can also be used. These magazines are described in U.S. Patent Nos. 4,834,306 and 5,226,613.

The above-described light-sensitive materials can also be advantageously used in lens-equipped film units described in JP-B No. 2-32,615 and JUM-B No. 39,784.

The processing layer of the processing material used in the present invention preferably contains a base or a base precursor.

The base and/or base precursor used in the present invention may be identical to or different from the decolorizing agent or a precursor thereof. In other words, the base (or base precursor) (e.g., a guanidine ring) necessary for imagewise production of a dye may or may not serve as a decolorizing agent (or the precursor of a decolorizing agent).

With respect to the base, inorganic bases or organic bases may be used. Examples of the organic bases include those described in JP-A No. 62-209448, such as alkali metal or alkaline earth metal hydroxides (e.g., potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide and magnesium hydroxide); alkali metal or alkaline earth metal phosphates (e.g., secondary or tertiary phosphates such as dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium sodium hydrogen phosphate and calcium hydrogen phosphate); alkali metal or alkaline earth metal carbonates (e.g., potassium carbonate, sodium carbonate, sodium hydrogen carbonate and magnesium carbonate); alkali metal or alkaline earth metal borates (e.g., potassium borate, sodium borate and sodium metaborate); and organic acid salts of alkali metals or alkaline earth metals (e.g., potassium acetate, sodium acetate, potassium oxalate, sodium oxalate, potassium tartarate, sodium tartarate, sodium malate, sodium palmitic acid and sodium stearate); as well as acetylides of alkali metals or alkaline earth metals described in JP-A No. 63-25208.

Examples of organic bases may include ammonia or aliphatic or aromatic amines such as primary amines (e.g., methylamine, ethylamine, butylamine, n-hexylamine, cyclohexylamine, 2-ethylhexylamine, allylamine, ethylenediamine, 1,4-diaminobutane, hexamethylenediamine, aniline, anisidine, p-toluidine, α-naphthylamine, m-phenylenediamine, 1,8-diaminonaphthalene, benzylamine, phenethylamine, ethanolamine, and thallium), secondary amines (e.g., dimethylamine, diethylamine, dibutylamine, diallylamine, N-methylaniline, N-methylbenzylamine, N-methylethanolamine, and diethanolamine); tertiary amines (e.g. N-methylmorpholine, N-hydroxyethylmorpholine, N-methylpyridine, N-hydroxyethylpiperidine, N,N'-dimethylpiperazine, N,N'-dihydroxyethylpiperazine, diazabicyclo[2.2.2]octane, N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N-methyldiethanolamine, N-methyldipropanolamine, triethanolamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetrahydroxyethylethylenediamine, N,N,N',N'-tetramethyltrimethylenediamine and N-methylpyrrolidine, the characteristics of which are described in JP-A No. 62-170954); polyamines (e.g. Diethylenetriamine, triethylenetetramine, polyethyleneimine, polyallylamine, polyvinylbenzylamine, poly(N,N-diethylaminoethyl methacrylate) and poly(N,N-dimethylvinylbenzylamine)); hydroxylamines (e.g. hydroxylamine and N-hydroxy-N-methylaniline); heterocyclic amines (pyridine, lutidine, imidazole, aminopyridine, N,N-dimethylaminopyridine, indole, quinoline, isoquinoline, poly(4-vinylpyridine) and poly(2-vinylpyridine)); Amidines (e.g. monoamidines such as acetoamidine, imidazoline, 2-methylimidazole, 1,4,5,6-tetrahydropyrimidine, 2-methyl-1,4,5,6-tetrahydropyrimidine, 2-phenyl-1,4,5,6-tetrahydropyrimidine, iminopiperidine, diazabicyclononene and diazabicycloundecene (DBU); and bis-, tris- or tetramidines); Guanidines (e.g. water-soluble monoguanidines such as guanidine, dimethylguanidine, tetramethylguanidine, 2-aminoimidazoline and 2-amino-1,4,5-tetrahydropyrimidine; water-insoluble mono- or bisguanidines described in JP-A No. 63-70845; and bis-, tris- or tetraguanidines); and tertiary ammonium hydroxides (e.g. tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trioctylmethylammonium hydroxide and methylpyridinium hydroxide).

Regarding the base precursors, those of decarburization acidification type, decomposition type, reaction type, complexing type can be used.

The invention, as described in EP-210,660 and US Patent No. 4,470,445, can preferably be used to form a base by combining a readily water-soluble basic metal compound and a compound capable of forming a complex compound with metal ions in the basic metal compound via water (called a complex compound). In this case, the readily water-soluble basic metal compound is preferably introduced into the photosensitive material and the complex compound is preferably introduced into the processing material, or vice versa. In particular, a method for forming guanidines can preferably be used, the formed guanidines also serving as an effective color decolorizing agent.

The amount of the base or its precursor can be 0.1 to 10 g/m², preferably 1 to 10 g/m².

Hydrophilic polymers used in the photosensitive material can also be used as binders in the processing layer.

The processing material is preferably hardened with a hardener as in the case of the photosensitive material. A hardener used in the photosensitive material may also be used. The processing material may contain a mordant. A polymer mordant is preferably used as the mordant. Examples of the mordant may include polymers having a secondary or tertiary amino group, polymers having an azo-heterocyclic moiety, and polymers having quaternary cationic groups thereof. These polymers have a molecular weight of 5,000 to 20,000, particularly 10,000 to 50,000.

Specifically, examples of the mordant include vinylpyridine polymer and cationic vinylpyridinium polymer disclosed in, for example, U.S. Patent Nos. 2,548,564, 2,484,430, 3,148,061 and 6,756,814; polymer mordants crosslinkable with gelatin described in, for example, U.S. Patent Nos. 3,625,694, 3,859,096 and 4,128,538 and British Patent No. 1,277,453; aqueous sol-type mordants disclosed in, for example, U.S. Patent Nos. 3,625,694, 3,859,096 and 4,128,538 and British Patent No. 1,277,453. e.g., U.S. Patent Nos. 3,958,995, 2,721,852 and 2,798,063 and JP-A Nos. 54-115228, 54-145529 and 54-126027; water-insoluble mordants disclosed in U.S. Patent No. 3,898,088; reactive mordants capable of forming covalent bonds with dyes disclosed in, e.g., U.S. Patent 4,168,976 (JP-A No. 54-137333); and mordants disclosed in U.S. Patent Nos. 3,709,690, 3,788,855, 3,624,482, 3,488,706, 3,557,066, 3,271,147 and 3,271,148 and in JP-A Nos. 50-71332, 53-30328, 52-155528, 53-125 and 53-1024.

Other mordants described in U.S. Patent Nos. 2,675,316 and 2,882,156 may also be used.

In the present invention, a development stopping agent may be incorporated into the processing material so that the agent acts simultaneously with development.

As used herein, a development stopper is a compound that directly neutralizes or reacts with a base to reduce the concentration of the bases contained in the film and thus stop development, or a compound that acts with silver or silver salts to inhibit development. Specific examples of the development stopping agent include acid precursors that release an acid upon application of heat, electrophilic compounds that cause a substitution reaction with a coexisting base, nitrogen-containing heterocyclic compounds, and mercapto compounds and their precursors. More specific examples are described in JP-A No. 62-253,159 on pages 31-32.

Further, the following is an advantageous composition: a zinc salt of mercaptocarboxylic acid described in JP-A No. 8-54,705 is introduced into the light-sensitive material, and one of the above-mentioned complexing compounds is introduced into the processing material.

Similarly, a pressure-preventing agent acting on silver halides may be contained in the processing material so that the agent acts during development. Examples of the pressure-preventing agent may include monohalogen compounds described in JP-B No. 54-164, trihalogen compounds described in JP-A No. 53-46,020, compounds described in JP-A 48-45,228 consisting of a halogen and aliphatic carbon atoms bonded to the halogen, and polyhalogen compounds typified by tetrabromoxylene described in JP-B 57-8,454. Development retarders, e.g., 1-phenyl-5-mercaptotetrazole described in British Patent No. 1,005,144, are also effective.

The amount of the pressure preventing agent is preferably 10-4 to 1 mol, more preferably 10-3 to 10-1 mol per mol of silver.

Alternatively, the processing agent may contain a physical development nucleus and the silver halide solvent, so that the silver halide solvent dissolves the silver halide contained in the light-sensitive material simultaneously with development and fixes the silver halide to the processing layer.

The physical development nucleus reduces the soluble silver salt which diffuses from the photosensitive material to convert it into physically developed silver, which is fixed to the processing layer. Any physical development nucleus known can be used in the present invention. Examples of the physical development nuclei include colloidal particles of heavy metal (such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper and ruthenium), a noble metal (such as palladium, platinum, silver and gold), a chalcogen compound composed of the foregoing and a substance such as sulfur, selenium and tellurium. These physical development nuclei are obtained by reducing a corresponding metal ion using a reducing agent such as ascorbic acid, sodium borohydride or hydroquinone to produce a colloidal dispersion of the metal, or by mixing the corresponding metal ion with a solution of soluble sulfide, selenide or telluride to produce a colloidal dispersion of insoluble metal sulfide, metal selenide or metal telluride. These colloidal grains are preferably prepared in a hydrophilic binder such as gelatin. The method for preparing the colloidal silver grains is described, for example, in U.S. Patent No. 2,688,601. If necessary, a desalting process may be carried out in the preparation of the colloidal silver, as is known in a method for preparing a silver halide emulsion in which excessive salt is removed.

The grain diameters of the physical development nuclei are preferably in the range of 2 to 200 nm.

The physical development nuclei are present in an amount in the range between 10⁻³ to 100 mg/m², preferably between 10⁻² 10 mg/m² in the processing layer.

Although the physical development nuclei can be prepared separately from a coating solution and the physical development nucleus can be subsequently added to the coating solution, the physical development nuclei can be prepared, for example, by the reaction between silver nitrate and sodium sulfite or between silver chloride and a reducing agent in a coating solution containing a hydrophilic binder.

Silver, silver sulfite, palladium sulfite is preferably used as a physical development nucleus. When the physically developed silver transferred into a processing material is used as an image, it is preferable to use palladium sulfite, silver sulfite because they have small Dmin and high Dmax values.

The solvent for silver halide may be a known compound, examples of which include thiosulfates (such as sodium thiosulfate and ammonium thiosulfate), sulfites (such as sodium sulfite and sodium hydrogen sulfite), thiocyanates (such as potassium thiocyanate and ammonium thiocyanate), thioethers (such as 1,8-di-3,6-dithiaoctane, 2,2'-thiodiethanol, 6,9-dioxa-3,12-dithiatetradecane-1,14-diol as described in JP-B No. 47-11,386), a compound having a 5- or 6-membered imido ring (such as uracil and hydantoin as described in Japanese Patent Application No. 6-325,350), and a compound represented by the following general formula (VI) as described in JP-A No. 53-144,319. A mesoionthiolate compound of trimethyltriazolinethiolate described in "Analytica Chemica Acta", vol. 248, pages 604 to 614 (1991) is also a preferable compound. A compound described in Japanese Patent Application No. 6-206,331, which is capable of fixing and stabilizing silver halide, can also be used as a solvent for silver halide.

N(R¹)(R²)-C(=S)-X-R³ (I)

wherein X represents a sulfur atom or an oxygen atom, each of R¹ and R², which may be the same or different from each other, represents an aliphatic group, an aryl group, a heterocyclic group or an amino group, R³ represents an aliphatic group or an aryl group, wherein R¹ and R² or R² and R³ may be bonded to each other to form a 5-membered or a 6-membered heterocyclic ring. The solvents for silver halide described above may be used in combination. Among the above-described compounds, a compound having a 5-membered or 6-membered imido ring such as sulfite, uracil or hydantoin is particularly preferred. The addition of uracil or hydantoin in the form of potassium salt is preferred because the salt can suppress gloss reduction during storage of the processing material.

The proportion of the total amount of the solvent for silver halide in the processing layer is in the range of 0.01 to 50 mmol/m², preferably 0.1 to 30 mmol/m³, and particularly preferably 1 to 20 mmol/m². The total amount of the solvent for silver halide in the photosensitive material is in the range of 1/20 to 20 times, preferably 1/10 to 10 times, and particularly preferably 1/3 to 3 times the amount (mol) of silver coated on the photosensitive material. When the solvent for silver halide is used, it may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide or methylpropyl glycol, or to an alkaline or acidic aqueous solution, or otherwise a dispersion comprising fine solid grains of the solvent for silver halide may be added to a coating solution.

Similar to the photosensitive material, the processing material can contain a variety of auxiliary layers, such as a protective layer, an underlayer, a backing layer.

The processing material is preferably constructed such that a processing layer is provided as a continuous fabric.

As used herein, the term "continuous web of the processing material" refers to a type in which the length of the processing material is significantly longer than the main side of the corresponding photosensitive material when processing is carried out, so that the processing material can be used without cutting off a piece thereof and is long enough to enable the processing of a variety of photosensitive materials. In general, the length of the processing material is 5 times or more of the width, but 1000 times or less of the width. Although the width of the processing material is arbitrarily determined, it is preferable that it is not shorter than the width of the corresponding photosensitive material.

According to another preferred manner, a plurality of photosensitive materials are processed in parallel. In this case, the width of the processing material is preferably equal to or more than "the width of the photosensitive material" times "the number of photosensitive materials processed in parallel".

Such a continuous web type processing material is particularly advantageous when the photosensitive material has a length of 50 cm or more, or when a plurality of photosensitive materials are continuously processed. Furthermore, when such a continuous web type processing material is used, the photosensitive material can be easily peeled off from the processing material.

The continuous web type processing material is preferably fed from a feed roller and taken out by being unwound from a roller. Especially in the case where the photosensitive material has a large size, this can make the disposal of the waste material very easy.

As described above, the continuous fabric type processing material significantly improves its handling compared with conventional sheet materials.

Although the thickness of the support used in the processing material of the present invention is arbitrarily determined, a thinner one is preferred. More preferably, the thickness is between 4 µm and 40 µm inclusive. If the thickness falls within this range, the amount of the processing material per unit area increases, so that the processing material roll becomes very compact.

The material of the support is not particularly limited, and any material that can withstand the temperatures during processing can be used. In general, a photographic support such as paper, a synthetic polymer (film) described in "Shashinkogaku no kiso Gin'en Shashin Hen (Fundamentals of Photographic Engineering - Silver Salt Photography Section)" pages 223-240, edited by Photographic Society of Japan and published by Corona Co., Ltd., 1979, is used. Specific examples of the support include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide and cellulose (e.g. triacetyl cellulose). Alternatively, the films in which pigments such as titanium dioxide are introduced, synthetic paper made of polypropylene, mixed paper and made of synthetic resin pulp and natural resin may be used. Pulp, smooth paper, baryta paper (photographic base paper) and coated paper (especially screen-coated paper).

These can be used individually or in combination. Alternatively, a synthetic polymer can be laminated to one or both sides of the paper to produce a carrier.

Other supports that can be used in the present invention include those described in JP-A No. 62-253,159, pages 29-31, 1-161,236 pages 14-17, 63-316,848, 2-22,651 and 3-56,955 and in U.S. Patent No. 5,001,033.

Furthermore, a carrier consisting mainly of a styrene-based polymer having a syndiotactic structure is preferred.

The surfaces of these supports may be coated with a hydrophilic binder and an antistatic agent such as carbon black and semiconductive metal oxides such as alumina sol and tin oxide. Aluminum coated supports may also be preferably used.

In the present invention, a preferable method for developing a photosensitive material used in photography with a camera, etc. may comprise applying a specific amount of water (10% to 100% of the amount necessary for maximum swelling of the entire coating film excluding the back layers of both the photosensitive material and the processing material) to the photosensitive material or the processing material, stacking the photosensitive material and the processing material, and then heating at a temperature between 60°C and 100°C for 5 to 60 seconds.

In the present invention, the photosensitive material and/or the processing material are attached to each other in a state of being swollen with water. Since the swollen film is unstable, it is critical that the amount of water is limited to the above range so as to prevent local unevenness in color development.

The amount of water necessary to achieve maximum swelling can be obtained by immersing the photosensitive material on which a coating film is located in water to measure it and when it is sufficiently swollen, measuring the film thickness and subtracting the weight of the coating film from the calculated maximum swelling volume. An example of measuring the swelling amount is also described in Photographic Science Engineering, Vol. 16, page 449 (1972).

In the present invention, it is preferably sought that the image information is obtained in the form of digital data using a scanner or similar device, whereby the developed silver produced during the development process and undeveloped silver halide are not removed. A conventional approach to the analog optical exposure process on a printing paper such as a color paper can also be used.

In the present invention, after photographing and subsequent image formation, other methods for preventing disadvantages against perfect reading of characters may also be used in combination. In particular, since undeveloped silver halide generates a strong fog in the gelatin layer to increase the density of the background of an image, the silver halide used in the present invention is considered to be advantageous in reducing such an effect. However, the detailed mechanism has yet to be determined by further studies.

To make prints on color paper or to use photosensitive materials for heat development using such color photographic materials, the methods described in JP-A Nos. 5-241,251, 5-19,364 and 5-19,363 can be used.

EXAMPLES

The present invention is described in detail below using examples.

Example 1: Preparation of a tabular silver iodobromide emulsion

(Step A): An aqueous solution (1,600 cc) containing gelatin (7.5 g) and KBr (4.3 g) was stirred while maintaining the temperature of the solution at 40°C. Aqueous 1.2 M AgNO3 solution (41 cc) and aqueous 1.4 M KBr/KI solution (41 ec) containing KI (12 mol%) were added simultaneously in two jets for 40 seconds. Gelatin (36 g) was added. Then the temperature of the mixture was raised to 58°C. Aqueous 0.4 M AgNO3 solution (36 cc) and subsequently ammonia were added. The mixture was aged for 15 minutes and neutralized with acetic acid. Aqueous 1.5 M AgNO3 solution (782 cc) and aqueous 1.9 M KBr solution (700 cc) were added for 17 minutes while maintaining the pAg at 8.4 and accelerating the feed rate (the feed at the time of completion of the addition was 4.2 times that at the time of initiation of the addition). Then, the resulting emulsion was cooled to 35°C and washed using a conventional flocculation method. Gelatin (49 g) was added so as to adjust the pH to 5.5 and the pAg to 8.8. The emulsion thus obtained contained 1.2 mol of silver and 65 g of gelatin per kg. The grains in the emulsion were tabular grains with a size of 0.27 µm.

(Step B): An aqueous solution (1,150 cc) containing the thus-obtained emulsion (30 g, which served as a seed emulsion), gelatin (33 g) and KBr (1.2 g) were stirred while the temperature of the mixture was kept at 75°C. 1.8 M AgNO3 aqueous solution (387 cc) and 1.6 M KBr/KI aqueous solution (427 cc) containing KI (10 mol%) were added over 38 minutes in two jets while accelerating the feed rate (the feed at the time of completion of the addition was 3.3 times higher than that at the time of initiation of the addition).

(Step C) Subsequently, the mixture was cooled to 55°C. 1 M AgNO3 aqueous solution (30 cc) and 0.2 M KI aqueous solution (100 cc) were added quantitatively over 3 minutes, and then KBr aqueous solution was added to adjust the pAg to 9.1. Then, 2 M AgNO3 aqueous solution (194 cc) and 2.2 M KBr aqueous solution (165 cc) were added. Subsequently, the resulting emulsion was cooled to 35°C and washed using a conventional flocculation method. Gelatin (75 g) was added to adjust the pH to 5.8 and the pAg to 8.9.

Tabular grains with a mean spherical diameter of 0.86 µm were obtained.

The emulsion thus obtained was subjected to spectral and chemical sensitization by adding the above-described spectral sensitizing dyes (blue-sensitive, green-sensitive and red-sensitive), Compound I, potassium thiocyanate, chloroauric acid and sodium thiosulfate at 60°C, pH = 6.2 and pAg = 8.4. The amount of chemical sensitizers was adjusted so as to maximize the sensitization for exposure to 1/100 second. Sensitizing dye IV for the blue-sensitive emulsion

6.0 · 10⊃min;⊃4; mol per mole of silver contained in the emulsion. Sensitizing dye I for the green-sensitive emulsion

5.3 · 10⊃min;⊃4; mol per mole of silver contained in the emulsion. Sensitizing dye II for the green-sensitive emulsion

1.2 · 10⊃min;⊃4; mol per mole of silver contained in the emulsion. Sensitizing dye III for the green-sensitive emulsion

4.5 · 10⊃min;⊃5; mol per mole of silver contained in the emulsion. Sensitizing dye V for the red-sensitive emulsion

2.4 · 10⊃min;⊃4; mol per mole of silver contained in the emulsion. Sensitizing dye VI for the red-sensitive emulsion

1.1 · 10⊃min;⊃5; mol per mole of silver contained in the emulsion. Sensitizing dye VII for the red-sensitive emulsion

3.4 · 10⊃min;⊃4; mol per mole of silver contained in the emulsion. Compound I

Preparation of a zinc hydroxide dispersion

Zinc hydroxide powder (31 g) with a primary grain size of 0.2 µm was mixed with dispersants, namely carboxymethyl cellulose (1.6 g) and sodium polyacrylate (0.4 g), lime-treated ossein gelatin (8.5 g) and water (158.5 ml). The dispersion was dispersed for one hour in a mill using glass beads. After the powder was dispersed, the glass beads were removed by filtration, thus obtaining a dispersion (188 g) of zinc hydroxide.

Preparation of emulsions containing a colour developing agent and a coupler

The oil phase components and the aqueous phase components shown in Table 1 were each dissolved to prepare a uniform solution at 60°C. The oil phase solution and the aqueous phase solution were combined and introduced into a 1-liter stainless container. Using a dissolver equipped with a disperser having a diameter of 5 cm, the mixture was stirred at 10,000 rpm for 20 minutes to thereby obtain a dispersion. Then, warm water as shown in Table 1 was added, followed by mixing at 2,000 rpm for 10 minutes. Thus, emulsions containing a cyan, magenta or yellow coupler and a color developing agent were prepared. Table 1 Cyan coupler (1) Magenta coupler (2) Yellow Coupler (3) Development resources (4) Antifogging agents (5) High boiling point solvents (6) Surfactant (7)

Production of color compositions for the filter layers

Color compositions to be introduced into the yellow, magenta and cyan filter layers were sequentially processed into emulsions and then added.

Briefly, the oil phase components and the aqueous phase components shown in Table 2 were each dissolved to prepare uniform solutions at 40°C. The oil phase solution and the aqueous phase solution were combined and homogenized in a homogenizer at 10,000 rpm for 5 minutes. Then, warm water as shown in Table 2 was added, followed by mixing at 2,000 rpm for 5 minutes. Table 2

Using the thus obtained materials, a photosensitive material I-101 having a multilayer structure as shown in Table 3 was prepared.

Furthermore, a processing material IR-1 as shown in Table 4 was also prepared. Table 3-1: Structure of photosensitive material I-101 Table 3-2: Structure of photosensitive material I-101 Surfactant (8) Surfactant (9) Water soluble polymer (10)

Hardeners (11)

CH2 =CH-SO2 -CH2 -SO2 -CH=CH2 Table 4: Processing material IR-1

Water soluble polymer (20):

SUMIKAGEL L-SH, from Sumitomo Chemical Co., Ltd.

Matting agents (22):

Polymethyl methacrylate (grain diameter: 4 um) Surfactant (23) Surfactant (24) Hardeners (25)

The photosensitive material I-101 thus prepared, which was cut to have the size of a conventional 135 negative film, perforated and placed in a camera, was used to photograph a person and a Macbeth diagram.

Water at 40°C was applied to the surface of the photosensitive layer of the photosensitive material used for photography in an amount of 15 cm/m² (corresponding to 45% of the volume of maximum swelling), and the water-applied surface was placed on the layer or film of the processing material IR-1. Heat was applied for 20 seconds from the back of the photosensitive material using a heat drum at 83°C. When the processing material IR-1 was peeled off from the photosensitive material I-101, a negative image was obtained on the photosensitive material. This image was read with a digital image reader FRONTIER SP-1000 (made by Fuji Photo Film Co., Ltd.), image-processed, and printed out using a heat development printer (PICTOGRAPHY 3000, Fuji Photo Film, Co., Ltd.). The prints of the person's figure showed excellent sharpness and graininess. If the photosensitive material has been similarly processed after three days stored at a humidity of 80%, excellent prints were obtained.

The dye compounds according to the present invention show excellent decolorizing properties in development, and the dyes were completely decolorized when subjected to processing. Furthermore, analysis of the processing material after processing showed that neither compounds of the present invention nor intermediates of guanidine picolinate (nucleophilic reagent, i.e. decolorizing agent) were present.

Furthermore, an unexpected effect of the addition of the dyes used in the present invention was obtained that the stability of the emulsion improved with time.

Comparison example 1:

Each of the following dyes (yellow, magenta and cyan; 4 g each) was combined with 25% aqueous solution (4 g) of a surfactant (30) and water (92 ml) and the mixture was processed for 24 hours in a DINOMILL using glass beads (average diameter: 0.75 mm). The glass beads were removed and a dispersion of each of the solid dyes was obtained. Yellow dye Magenta dye Cyan dye Surfactant (30

Using these dye dispersions, a photosensitive material I-102 was prepared. The photosensitive material I-102 contained the above-described solid dye dispersions in place of the yellow, magenta and cyan dyes contained in the photosensitive material I-101 prepared in Example 1.

When similar procedures as in Example 1, i.e., photographing, heat development, reading, image processing and printing were carried out using the photosensitive material I-102, prints of the figure of the person with excellent sharpness and graininess were obtained. When the photosensitive material I-102 was processed in a similar manner after being stored at 45ºC at a humidity of 80% for three days, the sensitivity of the photosensitive material deteriorated and gave images of poor quality because the images on the negative did not develop sufficient color.

Example 2

Photosensitive materials I-201 to I-205 were prepared in a similar manner, except that the magenta dye A-10 used in Example 1 (see Table 2) was replaced by the same molar amount of the dyes shown in Table 6.

When the materials were processed in the same manner as in Example 1, all materials produced images with excellent graininess and sharpness.

Table 6

Light-sensitive material Magenta dye

I-201 A-17

I-202 A-18

I-203 A-24

I-204 A-4

I-205 A-155

Example 3

Photosensitive materials I-301 to I-305 were prepared in a similar manner, except that the cyan dye A-26 used in Table 1 (see Table 2) was replaced by the same molar amount of the dyes shown in Table 6.

Table 7

Light-sensitive material Cyan dye

I-301 A-74

I-302 A-27

I-303 A-53

I-304 A-134

I-305 A-144

When these materials were processed in the same manner as in Example 1, the materials produced images with excellent graininess and sharpness.

Example 4

Photosensitive materials I-401 to I-406 were prepared in a similar manner except that the developing agent contained in the yellow developing layer, magenta developing layer and cyan developing layer as well as the couplers used in the photosensitive material I-101 in Example 1 were replaced with those shown in Table 8. The amounts of the respective substances were those shown in Example 1. Table 8

When the light-sensitive materials I-401 to I-406 were processed in the same manner as in Example 1, it was confirmed that the dye compositions according to the present invention were decolored as in Example 1 to provide prints with excellent quality.

Example 5 Production of light-sensitive silver halide emulsions

A process for preparing a blue-sensitive silver halide emulsion I-(1) is described below.

Distilled water (1.191 ml) containing gelatin (average molecular weight: 12,000; 0.96 g) and potassium bromide (0.9 g) were added to a reactor, and the ingredients were warmed to 40°C. An aqueous solution (A) (10.5 ml) containing silver nitrate (0.5 g) and an aqueous solution (B) (10 ml) containing potassium bromide (0.35 g) were added thereto with vigorous stirring over 150 seconds. Thirty seconds after the completion of the addition, 10% aqueous potassium bromide solution (12 ml) was added. Thirty seconds thereafter, the temperature of the reaction mixture was raised to 45°C. Lime-treated gelatin (35.0 g) and distilled water (250 ml) were added, followed by an aqueous solution (C) (39 ml) containing silver nitrate (10.0 g) and an aqueous solution (D) (30 ml) containing Potassium bromide (6.7 g) was added over 3 minutes and 15 seconds while increasing the addition rate. Then, an aqueous solution (E) (302 ml) containing silver nitrate (96.7 g) and an aqueous solution (F) containing potassium iodide and potassium bromide (molar ratio = 7:93, the concentration of potassium bromide: 26%) were added over 20 minutes while increasing the addition rate. During the addition, the silver potential of the reaction mixture was controlled to be -20 mV with respect to the saturated calomel electrode. Further, an aqueous solution (G) (97 ml) containing silver nitrate (24.1 g) and a 21.9% aqueous potassium bromide solution (H) were added over 3 minutes so that the silver potential of the reaction mixture was 25 mV with respect to the saturated calomel electrode. After completion of the addition, the reaction mixture was kept at 75°C for 1 minute, and then the reaction mixture was cooled to 55°C. Thereafter, 1N sodium hydroxide solution (15 ml) was added. Two minutes thereafter, an aqueous solution (I) (100 ml) containing silver nitrate (5 g) and an aqueous solution (J) (200.5 ml) containing potassium iodide (4.7 g) were added over 5 minutes. After completion of the addition, potassium bromide (7.11 g) was added, and the reaction mixture was kept at 55°C for 1 minute. An aqueous solution (K) (248 ml) containing silver nitrate (62 g) and an aqueous solution (L) (231 ml) containing potassium bromide (48.1 g) were added over 8 minutes. Thirty seconds thereafter, an aqueous solution containing sodium ethylthiosulfonate (0.03 g) was added, and the reaction mixture was cooled. By using Demol (product of Kao Corporation), the reaction mixture was desalted and allowed the emulsion grains to flocculate and precipitate. The grains were dispersed by adding sodium benzenethiosulfonate, phenoxyethanol, a water-soluble polymer (27) and lime-treated gelatin.

Chemical sensitization was carried out at 60ºC. A sensitizing dye (12) was dispersed in gelatin and the dispersion was added before chemical sensitization. After addition, a mixture of potassium thiocyanate and chlorauric acid was added. Then sodium thiosulfate and a selenium sensitizer were added. Chemical sensitization was stopped by adding the mercapto compounds. The amounts of sensitizing dye, chemical sensitizers and mercapto compounds were optimized by sensitivity and nebulization.

The emulsion thus obtained contained tabular grains in such an amount that it was more than 99% of the total projected area of the whole of the grains. The average spherical diameter of the grains was 1.07 µm, the average thickness was 0.38 µm, the average circular diameter was 1.47 µm and the average aspect ratio was 3.9. Sensitizing dye (12) Water soluble polymer (27 Selenium sensitizers Mercapto compound

A process for preparing a blue-sensitive silver halide emulsion I-(2) is described below.

Distilled water (1.191 ml) containing gelatin (average molecular weight: 12,000; 0.96 g) and potassium bromide (0.9 g) were added to a reactor and the ingredients were heated to 40°C. An aqueous solution (A) (37.5 ml) containing silver nitrate (1.5 g) and an aqueous solution (B) (37.5 ml) containing potassium bromide (1.051 g) were added with vigorous stirring over 90 seconds. Thirty seconds after the completion of the addition, a 10% aqueous solution of potassium bromide (12 ml) was added. Thirty seconds thereafter, the temperature of the reaction mixture was raised to 75°C. Lime-treated gelatin (35.0 g) and distilled water (250 ml) were added, and then an aqueous solution (C) (116 ml) containing silver nitrate (29.0 g) and an aqueous solution (D) (91 ml) containing potassium bromide (20 g) were added over 11 minutes and 35 seconds while increasing the addition rate. Then an aqueous solution (E) (302 ml) containing silver nitrate (96.7 g) and an aqueous solution (F) containing potassium iodide and potassium bromide (molar ratio = 3.3:96.7, the concentration of potassium bromide: 26%) were added over 20 minutes while increasing the addition rate. During the addition, the silver potential of the reaction mixture was controlled to be -2 mV with respect to the saturated calomel electrode. Further, an aqueous solution (G) (97 ml) containing silver nitrate (24.1 g) and a 21.9% aqueous potassium bromide solution (H) were added over 3 minutes so that the silver potential of the reaction mixture was 0 mV with respect to the saturated calomel electrode. After the completion of the addition, the reaction mixture was kept at 75°C for 1 minute and then the reaction mixture was cooled to 55°C. Then, 1 N sodium hydroxide solution (15 ml) was added. Two minutes thereafter, an aqueous solution (I) (153 ml) containing silver nitrate (10.4 g) and an aqueous Solution (J) (414.5 ml) containing potassium iodide (9.35 g) was added over 5 minutes. After the completion of the addition, potassium bromide (7.11 g) was added, and the reaction mixture was kept at 55 °C for 1 minute. An aqueous solution (K) (228 ml) containing silver nitrate (57.1 g) and an aqueous solution (L) (201 ml) containing potassium bromide (43.91 g) were added over 8 minutes. Thirty seconds thereafter, an aqueous solution containing sodium ethylthiosulfonate (0.04 g) was added, and the reaction mixture was cooled. Similar to the case of the blue-sensitive silver halide emulsion I-(1), the reaction mixture was desalted and the resulting grains were dispersed.

Chemical sensitization was carried out in the same manner except that the blue-sensitive silver halide emulsion I-(1) and the selenium sensitizer were not used. The amounts of the sensitizing dyes and the mercapto compounds for completing chemical sensitization were almost proportional to the surface area of the emulsion grains.

The emulsion thus obtained contained tabular grains in such an amount that it was more than 99% of the total projected area of the whole of the grains. The average spherical diameter of the grains was 0.66 µm, the average thickness was 0.17 µm, the average circular diameter was 1.05 µm, and the average aspect ratio was 6.3.

A process for preparing the blue-sensitive silver halide emulsion I-(3) is described below.

Distilled water (1.345 ml) containing lime-treated gelatin (17.8 g), potassium bromide (6.2 g) and potassium iodide (0.46 g) were added to a reactor and the ingredients were heated to 45°C. An aqueous solution (A) (70 ml) containing silver nitrate (11.8 g) and an aqueous solution (B) (70 ml) containing potassium bromide (3.8 g) were added thereto with vigorous stirring over 90 seconds. The reaction mixture was maintained at 45°C for 4 minutes. Then, the temperature of the reaction mixture was raised to 63°C. Lime-treated gelatin (24 g) and distilled water (185 ml) were added, followed by an aqueous solution (C) (208 ml) containing silver nitrate (73 g) and a 24.8% aqueous potassium bromide solution. (D) were added over 13 minutes while increasing the addition rate. During the addition, the silver potential of the reaction mixture was controlled to be 0 mV with respect to the saturated calomel electrode. After completion of the addition, the reaction mixture was maintained at 63°C for 2 minutes, and then the temperature of the reaction mixture was lowered to 45°C. Thereafter, 1 N sodium hydroxide solution (15 ml) was added. Two minutes thereafter, an aqueous solution (I) (60 ml) containing silver nitrate (8.4 g) and an aqueous solution (F) (461 ml) containing potassium iodide (8.3 g) were added over 5 minutes. Further, an aqueous solution (G) (496 ml) containing silver nitrate (148.8 g) and a 25% aqueous potassium bromide solution (H) were added over 47 minutes so that the silver potential of the reaction mixture was 20 mV with respect to the saturated calomel electrode. Thirty seconds after the completion of the addition, an aqueous solution containing potassium bromide (2 g) and sodium ethylthiosulfonate (0.06 g) was added and the reaction mixture was cooled. Similar to the case of the blue-sensitive silver halide emulsion I-(2), the reaction mixture was dispersed and the resulting grains were chemically sensitized.

The emulsion thus obtained contained hexagonal tabular grains having the average grain diameter represented by the mean spherical diameter of the grains of 0.44 µm, the mean thickness of 0.2 µm, the mean circular diameter of 0.53 µm, and the mean aspect ratio of 2.6.

A process for preparing the green-sensitive silver halide emulsion I-(4) is described below.

Distilled water (1.191 ml) containing gelatin (average molecular weight: 12,000; 0.96 g) and potassium bromide (0.9 g) were added to a reactor and the ingredients were heated to 40°C. An aqueous solution (A) (17.5 ml) containing silver nitrate (0.7 g) and an aqueous solution (B) (17.5 ml) containing potassium bromide (1.051 g) were added with vigorous stirring over 120 seconds. Thirty seconds after the completion of the addition, a 10% aqueous solution of potassium bromide (12 ml) was added. Thirty seconds thereafter, the temperature of the reaction mixture was raised to 75°C. Lime-treated gelatin (35.0 g) and distilled water (250 ml) were added, and then an aqueous solution (C) (116 ml) containing silver nitrate (19.0 g) and an aqueous solution (D) (461 ml) containing potassium bromide (10 g) were added over 7 minutes and 35 seconds while increasing the addition rate. Then an aqueous solution (E) (302 ml) containing silver nitrate (96.7 g) and an aqueous solution (F) containing potassium iodide and potassium bromide (molar ratio = 3.3 : 96.7, concentration of potassium bromide: 26%) were added over 20 minutes while increasing the addition rate. During the addition, the silver potential of the reaction mixture was controlled to 0 mV with respect to the saturated calomel electrode. Further, an aqueous solution (G) (97 ml) containing silver nitrate (24.1 g) and a 21.9% aqueous potassium bromide solution (H) were added over 3 minutes so that the silver potential of the reaction mixture was 0 mV with respect to the saturated calomel electrode. After the completion of the addition, the reaction mixture was kept at 75°C for 1 minute, and then the reaction mixture was cooled to 55°C. Thereafter, an aqueous solution (I) (122 ml) containing silver nitrate (8.3 g) and an aqueous solution (J) (323 ml) containing potassium iodide (7.48 g) were added over 5 minutes. After the completion of the addition, potassium bromide (7.11 g) was added, and the reaction mixture was kept at 55°C for 1 minute. An aqueous solution (K) (228 ml) containing silver nitrate (62.8 g) and an aqueous solution (L) (201 ml) containing potassium bromide (48.3 g) were added over 8 minutes and the reaction mixture was cooled. Similar to the case of the blue-sensitive silver halide emulsion I-(1), the reaction mixture was desalted and the resulting grains were dispersed.

Chemical sensitization was carried out in a similar manner, except that a mixture of sensitizing dyes (13), (14) and (15) was used instead of a sensitizing dye (12) in the blue-sensitive silver halide emulsion I-(1). The mixing ratio of the sensitizers (13), (14) and (15) was 12:2:1 (mol).

The emulsion thus obtained contained tabular grains in such an amount that it was more than 99% of the total projected area of the grains. The average spherical diameter of the grains was 0.85 µm, the average thickness was 0.26 µm, the average circular diameter was 1.25 µm and the average aspect ratio was 4.8. Sensitizing dye (13) for the green-sensitive emulsion Sensitizing dye (14) for the green-sensitive emulsion Sensitizing dye (15) for the green-sensitive emulsion

A process for preparing the green-sensitive silver halide emulsion I-(5) is described below.

The formation of grains in salts and emulsification were carried out in a manner similar to that used in the preparation of the blue-sensitive silver halide emulsion, except that sodium hydroxide and sodium thiosulfate were not added in the grain formation step.

Chemical sensitization was also carried out in a similar manner to the green-sensitive silver halide emulsion I-(4).

The emulsion thus obtained contained tabular grains in such an amount that it was more than 99% of the total projected area of the whole of the grains. The average spherical diameter of the grains was 0.66 µm, the average thickness was 0.17 µm, the average circular diameter was 1.05 µm and the average aspect ratio was 6.3.

A process for preparing the green-sensitive silver halide emulsion I-(6) is described below.

The grain formation, desalting and emulsification were carried out in a manner similar to that used in the preparation of blue-sensitive silver halide emulsion I-(3), except that sodium hydroxide was not added and sodium ethyl thiosulfate (4 mg) was added during the grain preparation step.

Chemical sensitization was also carried out in a similar manner to the sensitization of the green-sensitive silver halide emulsion I-(4), except that a selenium sensitizer was not added.

The emulsion thus obtained contained hexagonal tabular grains having an average grain size represented by the spherical diameter of the grains of 0.44 µm, the average thickness of 0.2 µm, the average circle-corresponding diameter of 0.53 µm and the average aspect ratio of 2.6.

A process for preparing the red-sensitive silver halide emulsion I-(7) is described below.

Emulsion I-(7) was prepared in a similar manner to the preparation of green-sensitive silver halide emulsion I-(4), except that a gelatin dispersion of the sensitizing dye (16) and a gelatin dispersion of a mixture of the sensitizing dye (17) and the sensitizing dye (18) were added during chemical sensitization. The mixing ratio of the sensitizer (16), (17) and (18) was 40 : 2 : 58 (mol).

The emulsion thus obtained contained tabular grains in such an amount that it constituted more than 99% of the total projected area of the total of the grains. The average spherical diameter of the grains was 0.85 µm, the average thickness was 0.2 µm, the average circular diameter was 1.25 µm and the average aspect ratio was 4.8. Sensitizing dye (16) for red-sensitive emulsion Sensitizing dye (17) for the red-sensitive emulsion Sensitizing dye (18) for the red-sensitive emulsion

A method for preparing the red-sensitive silver halide emulsion I-(8) is described below.

Emulsion I-(8) was prepared in a manner similar to that used in the preparation of green-sensitive silver halide emulsion I-(5), except that a gelatin dispersion of the sensitizing dye (16) and a gelatin dispersion of a mixture of the sensitizing dye (17) and the sensitizing dye (18) were added during chemical sensitization. The mixing ratios of the sensitizers (16), (17) and (18) were 40:2:58 (mol).

The emulsion thus obtained contained tabular grains in such an amount that it constituted more than 99% of the total projected area of the entire grains. The mean spherical diameter of the grains was 0.66 µm, the mean thickness was 0.17 µm, the mean circular diameter was 1.05 µm and the mean aspect ratio was 6.3.

A process for preparing a red-sensitive silver halide emulsion I-(9) is described below.

Emulsion I-(9) was prepared in a manner similar to that used in the preparation of green-sensitive silver halide emulsion I-(6), except that a gelatin dispersion of sensitizing dye (16) and a gelatin dispersion of a mixture of sensitizing dye (17) and sensitizing dye (18) were added during chemical sensitization.

The emulsion thus obtained contained hexagonal tabular grains with the average grain size represented by the spherical diameter of the grains of 0.44 µm, the average thickness of 0.2 µm, the average circle-equivalent diameter of 0.53 µm, and then the average aspect ratio of 2.6.

Preparation of the emulsified dispersion of the colour developing agents and the couplers

The compositions of a cyan emulsion used in the third layer described in Table 11, a magenta emulsion used in the sixth layer described in Table 11 and a yellow emulsion used in the tenth layer described in Table 11 are shown in the following Table 9. Table 9 Yellow Coupler (28) Development funds (29)

The oil phase components and the aqueous phase components shown in Table 9 were each dissolved to obtain homogeneous solutions at 60°C. The oil phase solution and the aqueous phase solution were combined in a 1-liter stainless steel container equipped with a dissolver, a disperser (5 cm in diameter) and dispersed at 10,000 rpm for 20 minutes. Then, slightly hot water was added to the resulting mixture in a volume shown in Table 9 and the mixture was stirred at 2,000 rpm for 10 minutes. Then, coupler emulsions for three colors; cyan (the third layer), magenta (the sixth layer) and yellow (the tenth layer) were prepared.

Other emulsions were prepared in the same way.

Preparation of the color compositions for a yellow filter layer and an antihalation layer

Dye compositions were prepared as emulsions by the following procedure.

Leuco dyes, a developer and, if necessary, a high boiling point organic solvent were weighed and ethyl acetate was added. The resulting mixture was heated to 60ºC to dissolve to prepare a uniform solution. To this solution (100 cm³) were added the surfactant (7) (1.0 g) and 6.6% aqueous solution of lime-treated gelatin, heated to approximately 60ºC (190 cm³). The mixture was dispersed with a homogenizer for 10 minutes at 10,000 rpm to obtain two dye dispersions shown in Table 10. Table 10 Leuco dye Y Leuco dye B Leuco dye M oil (1) developer

Oil (1)

C₂₆H46·9Cl7·1

Manufacturing a carrier

The carrier used in the present invention was prepared as follows:

Polyethylene-2,6-naphthalate (PEN) polymer (100 parts by weight) was combined with Tinuvin P.326 (Ciba-Geigy; a light stabilizer, 2 parts by weight) and dried. The compound was melted at 300°C and extruded through a T-shaped die. The extruded material was subjected to longitudinal drawing (x 3.3) at 140°C and then to transverse drawing (x 3.3) at 130°C. The resulting drawn film was thermally heated at 250°C for 6 seconds to obtain a PEN film with a thickness of 92 µm. To the PEN film thus obtained, blue dyes, magenta dyes or yellow dyes (I-1, I-4, I-6, I-24, I-26, I-27 and II-5 described in Technical Disclosure Bulletin No. 94-6023) were added to give a yellow concentration of 0.01, a magenta concentration of 0.08 and a cyan concentration of 0.09. The film was wound on a stainless steel rod having a diameter of 20 cm and thermal hysteresis was applied at 113°C for 30 hours to obtain a support resistant to curling.

Coating a sublayer

The support thus obtained was subjected to corona discharge treatment, UV discharge treatment and annealing treatment on both surfaces. On the surface on which a photosensitive layer was provided, an undercoat liquid (10 cc/m²) containing gelatin (0.1 g/m²), sodium α-sulfodi-2-ethylhexylsuccinate (0.01 g/m²), salicylic acid (0.025 g/m²), PQ-1 (0.005 g/m²) and PQ-2 (0.006 g/m²) was applied using a mordant coater to provide an undercoat layer, which was then dried at 115°C for 6 minutes. (The temperature of the entire rollers and conveyors in the drying zone was preset to 115°C.)

Applying a backing layer 1) Applying an antistatic layer

An antistatic layer was formed by applying a mixture containing a fine powder dispersion (0.027 g/m2; diameter of secondary aggregates: about 0.08 µm, specific resistance: 5 Ω·cm) of tin IV-antimony oxide complex particles with an average diameter of 0.005 µm, gelatin (0.003 g/m2), (CH2=CHSO2CH2CH2NHCO)2CH2 (0.02 g/m2), polyoxyethylene (polymerization degree: 10)-p-nonylphenol (0.005 g/m2), PQ-3 (0.008 g/m2) and resorcinol.

2) Applying a magnetic recording layer

A magnetic recording layer having a thickness of 1.2 µm was formed by applying, using a roll coater, a mixture containing cobalt-γ-iron oxide (0.06 mg/m2; 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 surfaces are treated with alumina-silica (2 wt% with respect to the weight of iron oxide)) coated with 3-polyoxyethylene (polymerization degree: 15)-propyloxytrimethoxysilane (15 wt%), diacetyl cellulose (1.15 g/m2; the iron oxide was dispersed by using an open kneader and a sand mill), PQ-4 (0.075 g/m²) and PQ-5 (0.004 g/m²) as hardeners and solvents therefor (acetone, methyl ethyl ketone, cyclohexanone and dibutyl phthalate). The magnetic recording layer also contained a lubricant C₆H₁₃OH(OH)C₁₀H₂₀COOC₄₀H₈₁ (50 mg/m²), a matting agent of silica particles (5 mg/m²; average particle size: 1.0 µm) and an abrasive of alumina particles (15 mg/m²; average particle size: 0.44 µm, ERC-DBM, Reynolds Metal). Drying was carried out at 115°C for 6 minutes (the temperature of the entire rollers and conveyors in the drying zone was preset to 115°C). The increase in color density of DB in the magnetic recording layer upon irradiation with light from an X-light (blue filter) was approximately 0.1. The saturation magnetization moment of the magnetic recording layer was 4.2 emu/g, the coercive force was 7.3 x 10⁴ Å/m, and the square ratio was 65%.

3) Applying a sliding or lubricating layer

A mixture containing hydroxyethyl cellulose (25 mg/m²), PQ-6 (7.5 mg/m²), PQ-7 (1.5 mg/m²) and polydimethylsiloxane (1.5 mg/m²) was applied. The mixture was prepared by melting the respective ingredients in xylene/propylene glycol monomethyl ether (1/1) at 105ºC, pouring the resulting melt into propylene monomethyl ether (10 times the amount) at ambient temperature to form a dispersion and further dissolving the resulting dispersion in acetone (average particle size: 0.01 µm). Drying was carried out at 115ºC for 6 minutes (the rolls and conveyors in the drying zone were all preheated to 115ºC). The resulting sliding layer had excellent properties; a dynamic friction coefficient of 0.10 (stainless steel balls with a diameter of 5 mm, load: 100 g and speed: 6 cm/min), a static friction coefficient of 0.09 (nlipp method) and a dynamic friction coefficient of 0.18 against an emulsion layer, which is described below.

The compounds PQ-1 to PQ-7 used in the layers of the above support are described below.

The photosensitive material I-501 having a multilayer structure to serve as a color negative film was prepared by simultaneously depositing all the layers shown in Table 11 using the materials and support described above. Table 11-1: Structure of photosensitive material I-501 Table 11-2: Structure of photosensitive material I-501 Table 11-3: Structure of photosensitive material I-501 Table 11-4:

The total amount of potassium ions contained in the prepared light-sensitive material was 2.2 x 10-4 in terms of the amount of silver on a weight basis.

The processing material IR-2, the proportions of which are shown in Tables 12 and 13, was also prepared. Table 12: Structure of the processing material IR-2 Table 13: Structure of carrier A

Samples I-502 to I-512 were prepared by changing the leuco dye Y in the ninth layer (yellow filter layer) of the prepared sample I-501 with an equimolar of the dyes (listed in Table 14) used in the present invention, with the proviso that the developer incorporated in the ninth layer of I-501 was not used in Samples I-502 to I-512.

The prepared samples I-502 to I-512 were subjected to image-forming exposure and then subjected to the following thermal development process. The photosensitive materials were immediately after processing dried. The yellow density of each sample was determined using the corresponding fog value at an exposure dose having a yellow density expressed by [(fogging of sample I-501) + 2.0]. The results are shown in Table 14 as relative values, with the yellow density of sample I-501 taken as 100. The calculated relative values are used as an indication of the BL color developing ability of BL.

MTF (modulation transfer function) values at the yellow image 20 cycles/mm (sharpness of BL) were measured by a conventional MTF method under similar processing conditions. The results are shown in Table 14, with the data given by relative values taking sample I-501 as 100.

Development process

The development process comprised the following steps: supplying water at 40ºC (15 cm³/m², corresponding to 45% of the maximum swelling of a photosensitive material) to the exposed photosensitive material; laminating the resulting photosensitive material with the processing material IR-2; heating the photosensitive material from the back side with heat at 83ºC for 17 seconds; and peeling the photosensitive material from the processing material IR-2. Table 14

Table 14 shows that the light-sensitive material having a yellow filter layer containing the dye to be used in the present invention exhibits excellent sharpness without losing the color developability of BL during heat development.

Example 6:

Sample I-601 was prepared by changing the composition of the first layer (antihalation layer) of Sample I-501 to the composition shown in Table 15. Further, the cyan dye A-26 in Sample I-601 was replaced with the dyes (shown in Table 16) consisting of the present invention to provide Samples I-602 to I-609. Table 15 Table 16

The degree of color formation and sharpness of RL of each of the prepared samples I-601 to I-609 and the sample I-501 were determined after they were processed in a similar manner as used in Example 5. As also found in Example 5, when the dyes according to the present invention are used, it was found that they provide a light-sensitive material which provides excellent sharpness of RL without losing the color developing ability of RL.

Example 7:

Sample I-701 was prepared by changing the 9th layer of Sample I-601 from Example 6 in a similar manner to that in Example 5 for Sample I-502;

and by modifying the fifth layer as shown in Table 17. Furthermore, the dye A-26 in the first layer, the dye A-10 in the fifth layer, and the dye A-3 in the ninth layer of sample I-701 were substituted for the dyes shown in Table 18 to provide samples I-702 to I-716. The degree of color formation and sharpness was measured by a similar method as in Example 5. All the samples showed excellent sharpness without reducing the color developability. Table 17 Table 18

Example 8: A process for preparing tabular silver iodobromide emulsions (for comparison) II-M-1, II-M-2 and II-M-3 is described below.

Distilled water (930 ml) containing gelatin (average molecular weight: 15,000; 0.74 g) and potassium bromide (0.7 g) were added to a reactor, and the ingredients were heated to 42°C. An aqueous solution (30 ml) containing silver nitrate (1.0 g) and an aqueous solution (30 ml) containing potassium bromide (0.82 g) were added with vigorous stirring for 30 seconds. After completion of the addition, the temperature of the reaction mixture was maintained at 40°C for 1 minute, and then raised to 75°C. Gelatin (27.5 g) and distilled water (200 ml) were added, followed by an aqueous solution (100 ml) containing silver nitrate (22.5 g) and an aqueous solution (80 ml) containing Potassium bromide (15.43 g) was added over 11 minutes while increasing the addition rate.

Subsequently, an aqueous solution (250 ml) containing silver nitrate (75.1 g) and an aqueous solution containing potassium iodide and potassium bromide (molar ratio = 3:97, the concentration of potassium bromide was 26%) were added over 20 minutes while increasing the addition rate. During the addition, the silver potential of the reaction mixture was controlled to 2 mV with respect to the saturated calomel electrode. Further, an aqueous solution (75 ml) containing silver nitrate (18.7 g) and a 21.9% aqueous potassium bromide solution were added over 4 minutes so that the silver potential of the reaction mixture was 0 mV with respect to the saturated calomel electrode. After the completion of the addition, the reaction mixture was kept at 73°C for 1 minute, and then the reaction mixture was cooled to 55°C. Then, an aqueous solution (120 ml) containing silver nitrate (8.1 g) and an aqueous solution (320 ml) containing potassium iodide (7.26 g) were added over 5 minutes. After the completion of the addition, potassium bromide (5.5 g) and potassium hexachloroiridate (0.04 mg) were added, and the reaction mixture was kept at 55°C for 1 minute. Further, an aqueous solution (180 ml) containing silver nitrate (44.3 g) and an aqueous solution (160 ml) containing potassium bromide (34.0 g) were added over 10 minutes. The reaction mixture was cooled and desalted by a conventional method.

The obtained emulsion was a silver iodobromide emulsion (silver iodide content: 5.7 mol%) formed of tabular hexagonal grains. The mean diameter of the grains corresponding to a circle was 1.81 µm, and the mean aspect ratio (obtained by dividing the mean grain diameter by the mean thickness) was 3.8. This emulsion is referred to as Emulsion II-M-1.

Emulsions II-M-2 and Emulsions II-M-3 were prepared from grains having a circle diameter of 1.21 µm and 0.76 µm, the grains being prepared using different initial amounts of gelatin and potassium bromide than those used in the preparation of Emulsion II-M-1. Emulsions II-M-2 and Emulsions II-M-3 were used in Example 9.

A process for preparing cubic silver chloride emulsions (for comparison purposes) II-R-1, II-R-2 and II-R-3 is described below.

Distilled water (1000 ml) containing calcium-removed gelatin (calcium content: not more than 2000 ppm, 30.0 g), sodium chloride (2.4 g) and sulfuric acid (1 N, 15.0 ml) were added to a reactor and the ingredients were heated to 59°C. An aqueous solution (concentration 1%, 1.91 ml) of N,N'-dimethylimidazolidine-2-thione, an aqueous solution (2000 ml) containing silver nitrate (7.1 g) and an aqueous solution (2000 ml) containing sodium chloride (2.41 g) were added thereto with vigorous stirring over 24 minutes. Further, an aqueous solution (500 ml) containing silver nitrate (162.8 g) and an aqueous solution (500 ml) containing sodium chloride (59.88 g) were added over 80 minutes while increasing the rate of addition. 60 minutes after the start of addition of this reaction mixture, potassium hexachloroiridate (0.04 mg) was added. After the completion of the addition, the temperature of the reaction mixture was maintained at 55°C for 5 minutes. Then, the reaction mixture was cooled and desalted by a conventional method.

The emulsion thus obtained consisted of cubic grains with a mean diameter of 0.73 µm corresponding to a circle. The emulsion is referred to as Emulsion II-R-1.

Emulsion II-R-2 and Emulsion II-R-3 were prepared in a similar manner as used in the preparation of Emulsion II-R-1, except that the temperature of the reactors was 45°C and 40°C. The average diameters of the grains of the obtained Emulsions II-R-2 and II-R-3 were 0.54 µm and 0.29 µm. Emulsion II-R-2 and Emulsion II-R-3 were used in Example 1.

Processes for preparing higher AgCl tabular silver chlorine emulsions (present invention) II-H-1, II-H-2 and II-H-3 having (100) major faces are described below.

Distilled water (1000 ml) containing gelatin (average molecular weight: 15000; 20.2 g), sodium chloride (0.81 g) and sulfuric acid (1 N, 8.8 ml) were added to a reactor and the ingredients were heated to 35°C. An aqueous solution (30 ml) containing silver nitrate (6.1 g) and an aqueous solution (30 ml) containing sodium chloride (2.00 g) and potassium bromide (0.21 g) were added to the reaction mixture with vigorous stirring over 45 seconds. An aqueous solution containing polyvinyl alcohol (average polymerization degree: 300 to 700, 5.0 g of Kuraray Poval 105; Kuraray Co., Ltd.) was added to the reaction mixture. Then, an aqueous solution (40 ml) containing sodium bromide (0.55 g) was added. Further, an aqueous solution (100 ml) containing silver nitrate (18.3 g) and an aqueous solution (100 ml) containing sodium chloride (6.30 g) were added over 3 minutes. After adding sodium hydroxide (1 N, 6.0 ml), the temperature of the reaction mixture was raised to 75°C. After gelatin (10.0 g) and distilled water (100 ml) were added, an aqueous solution (760 ml) containing silver nitrate (145.4 g) and an aqueous sodium chloride solution (7.0%) were added over 45 minutes while increasing the addition rate so that the silver potential of the reaction mixture was controlled to 100 mV with respect to the saturated calomel electrode. Potassium hexachloroiridate (0.05 mg) was added and the temperature of the reaction mixture was kept at 75°C for 30 minutes. The reaction mixture was then cooled and desalted by a conventional method.

The obtained emulsion was a (100) silver chlorobromide emulsion (silver bromide content: 0.64 mol%) formed from tabular grains. The grains had an average circle-equivalent diameter of 0.67 µm, an average aspect ratio of 7.1 (obtained by dividing the circle-equivalent diameter by the average thickness), and an average ratio of the adjacent sides of the rectangular projection areas of 1:1.25. This emulsion is referred to as emulsion II-H-1. By controlling the molecular weight and the amount of gelatin used in the first reaction, emulsions having average sphere-equivalent diameters of 0.50 µm and 0.31 µm (III-H-2 and II-H-3) were prepared. The obtained Emulsion II-H-2 and Emulsion II-H-3 were used in Example 9.

Spectral sensitization and chemical sensitization of emulsions II-M-1, II-M-2, II-M-3, II-R-1, II-R-2, II-R-3, II-H-1, II-H-2 and II-H-3 are described below. To these emulsions, spectral sensitizing dyes (II-I, II-II and II-III) mentioned below, compound II-I, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to effect spectral sensitization and chemical sensitization. In this case, the spectral sensitizing dyes were varied in proportion to the grain surface area of each emulsion. The amounts of pAg and chemical sensitizers at the time of chemical sensitization were controlled to achieve an optimum level of chemical sensitization for each emulsion. The green-sensitive emulsions thus obtained are represented by II-M-1g and the like with a small letter g. Sensitizing dye II-I for the green-sensitive emulsion

8.4 · 10⊃min;⊃4; mol per mol of silver for each emulsion Sensitizing dye II-II for the green sensitive emulsion

2.2 · 10⊃min;⊃4; mol per mol of silver for each emulsion Sensitizing dye II-III for the green sensitive emulsion

3.2 · 10⊃min;⊃4; mol per mole of silver for each emulsion compound II-I

Processes for preparing tabular emulsions (present invention) II-B-1, II-B-2 and II-B-3 having (111) major faces with high AgCl content are described below.

An aqueous gelatin solution (1200 ml) containing deionized alkali-treated bone gelatin (2.1 g) and sodium chloride (2 g) was added to a reactor and the temperature was maintained at 35°C. To this reaction mixture, 60 ml of an aqueous solution (A) (1100 ml) containing silver nitrate (165 g) and 60 ml of an aqueous solution (B) (1100 ml) containing sodium chloride (59.1 g) were simultaneously added under vigorous stirring over 1 minute. An aqueous solution (C) (50 ml) containing the compound (3) (0.285 g) was prepared. One minute after the completion of the addition of this solution (40 ml), 10% aqueous sodium chloride solution (30 ml) was added. After the addition, the temperature of this reaction mixture was raised to 60°C over 25 minutes, and 16 minutes thereafter, an aqueous gelatin solution (260 ml) containing phthalic acid treated gelatin (29 g) was added. Three minutes thereafter, solution (C) (10 ml) was added. One minute later, solution (A) (768 ml) and solution (B) (768 ml) were added simultaneously to the reaction mixture at an initial rate of 2.85 ml/min and an acceleration of 0.818 ml/min2. Ten minutes before the completion of the addition of solution (A) and solution (B), an aqueous solution (D) (270 ml) containing sodium chloride (3.9 g) and yellow prussiate of potash (0.1 g) was added over 10 minutes. Two minutes before the completion of the addition of the solution (A) and the solution (B), 10% aqueous potassium bromide solution (34 ml) was added over 3 minutes. Three minutes after the completion of the addition of the solution (A) and the solution (B), 1% aqueous sodium thiosulfate solution (45 ml) was added and the solution (45 ml) of a gelatin dispersion (gelatin content: 100 g) containing the above-mentioned sensitizing dyes for a green-sensitive emulsion, i.e., II-I (570 mg), II-II (60 mg) and II-III (120 mg) was added to the reaction mixture. After 1 minute of addition, the temperature of the mixture was raised to 75°C and the mixture was kept at this temperature for 10 minutes. Then, the mixture was cooled to 40°C and desalted by a conventional method using a precipitating agent (1). Deionized alkali-treated bone gelatin (67 g), zinc nitrite and phenoxyethanol were used to obtain a dispersion of the mixture. The pH and pAg were adjusted to 6.3 and 7.7, respectively.

The grains contained in the obtained emulsion were tabular (111) silver chlorobromide grains (silver bromide content: 5 mol%) and had an average sphere-like diameter of 0.74 µm, an average aspect ratio of 8.7 and an average ratio of adjacent sides of projected areas of 1:1.6. This emulsion is referred to as Emulsion II-B-1. Chemical sensitization of this Emulsion II-B-1 was carried out at 60°C with subsequent addition of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, sodium thiosulfate, selenium sensitizer, chloroauric acid and sodium benzenethiosulfate to achieve a maximum level of chemical sensitization. The compound (4) was used to interrupt the chemical sensitization. The green-sensitive emulsions thus obtained are represented by II-B-1g and the like, with a small letter g. Compound (3) Precipitants (1) Connection (4) Selenium sensitizer mixture of

and

(Molar ratio = 3 : 1)

Furthermore, the initial amount of gelatin, the silver nitrate content of the solution (A) and the sodium chloride content of the solution (B) were adjusted to prepare emulsions II-B-2 g and II-B-3 g which had (111) major faces and whose grain size was different from the grain size of the emulsion II-B-1 g. The grains of the emulsions II-B-2 g and II-B-3 g were 0.51 µm and 0.3 µm. These emulsions II-B-2 g and II-B-3 g were used in Example 9.

A dispersion of zinc hydroxide to be used as a base precursor was prepared.

Zinc hydroxide powder (31 g) with a primary grain size of 0.2 µm was mixed with dispersants, namely carboxymethyl cellulose (1.6 g) and sodium polyacrylate (0.4 g), lime-treated ossein gelatin (8.5 g) and water (158.5 ml). The mixture was dispersed for 1 hour in a mill using glass beads. After the powder was dispersed, the glass beads were removed by filtration, thus obtaining a dispersion (188 g) of zinc hydroxide.

A magenta coupler emulsion was prepared as follows.

Magenta coupler (a) (7.80 g), developing agent (b) (5.45 g), antifoggant (c) (2 mg), high boiling point organic solvent (d) (8.21 g) and ethyl acetate (24.0 ml) were mixed and dissolved at 60°C. The resulting solution was mixed with an aqueous solution (150 g) containing lime-treated gelatin (12.0 g) and Sodium dodecylbenzenesulfonate (0.6 g). The mixture was emulsified using a dissolving stirrer at 10,000 rpm for 20 minutes while maintaining the temperature at 50°C. After completion of emulsification, distilled water was added to make a total of 300 g. The mixture was stirred at 2,000 rpm for 10 minutes.

A dye dispersion for a magenta layer (invention) was prepared by using the following emulsion method. Briefly, an oil phase containing the aforementioned magenta dye A10 (2.0 g), tricresyl phosphate (2.0 g) and cyclohexane (22 cm³) and an aqueous phase containing lime-treated gelatin (3.5 g), surfactant (e) (0.26 g) and water (37 cm³) were mixed. The mixture was dispersed with a homogenizer at 10,000 rpm for 3 minutes at 40°C. Water (44 cm³) was further added and the mixture was stirred at 2,000 rpm for 10 minutes to obtain a uniform dispersion.

The obtained dispersion contained grains with an average grain size of 0.18 µm.

For comparison purposes, a colored dispersion product was prepared to be incorporated into a layer forming a colored layer capable of being decolored during a heat development process. Into this colorant dispersion, a magenta leuco dye and zinc were incorporated in combination.

These dispersions and the previously prepared silver halide emulsions were used in combination to prepare six heat-developable color photographic light-sensitive materials of Samples II-101 to II-106, which are shown in Table 19.

Similarly, processing materials II-P-1 and II-P-2 shown in Tables 20 to 22 were prepared. Table 19 Table 19 Note surfactant (f) Surfactant (g) Water soluble polymer (h)

Hardener (i)

CH₂=CH-SO₂-CH₂-SO₂-CH=CH₂ Table 20: Structure of processing material II-P-1 Table 21: Structure of processing material II-P-2 Table 22: Structure of carrier A Matting agent (m): SYLOID 79 (Fuji Devison) High boiling point solvent (s): ENPARA (Ajinomoto KK)

These photosensitive materials were exposed to light through a green filter using an optical wedge (1000 lux for 1/100 sec.).

Warm water (40°C, 18 ml/m²) was applied to the surface of the exposed photosensitive material, and this surface was placed on the surface of the processing material II-P-1 in a superimposed manner. Heat was applied to this using a heat drum at 83°C for 50 seconds. Then, a photosensitive material was peeled off to confirm that a wedge-shaped image developing magenta color was obtained.

For fixing purposes, a second step was carried out using the processing material II-P-2. Briefly, in the second step, water (12 cm³/m²) was applied to the processing material II-P-2, the surface of the wet material was bonded in an opposite manner to the previously processed (first step) photosensitive material, and the integrated body was heated at 70ºC for 20 seconds.

When the unexposed areas of the obtained samples were visually examined, it was found that all the color layers were completely decolored. The transmission density of each of the colored samples was measured and the sensitivity of each photosensitive material was determined using a so-called characteristic curve. When the relative sensitivity was expressed by an inverse number of the amount of exposure corresponding to the density of 0.15 higher than the fog density, the photosensitive materials II-101 to II-106 all fell within the same range with variations within ± 0.1. Therefore, it is found that these photosensitive materials had almost identical sensitivities.

The maximum density of these samples was measured. In all cases, bleaching of the silver halide was not carried out. In both cases of the presence or absence of the fixing process, almost the same results could be obtained. The results obtained in the case of the absence of the fixing process are shown in Table 23. Table 23

Table 23 shows that the photosensitive materials of the present invention show an increased maximum density and are therefore excellent photosensitive materials. When the photosensitive material and the processing material were each extracted by liquid chromatography, the dyes which were decolored remained in the photosensitive material and were not transferred to the processed material.

Example 9:

By changing the spectral sensitizing dyes used in Example 8 to spectrally sensitize the silver halide emulsions to those shown below, blue-sensitive and red-sensitive emulsions were prepared. The blue-sensitive emulsion and the red-sensitive emulsion were respectively designated by, for example, II-M-1b and II-M-1r using a "b" or "r" at the end. Blue-sensitive dye IV for the blue-sensitive emulsion

6.0 · 10⊃min;⊃4; mol per mol of silver for each (-b) emulsion Red-sensitive dye V for the red-sensitive emulsion

3.5 · 10⊃min;⊃4; mol per mol of silver for each emulsion Red-sensitive dye V for the red-sensitive emulsion

1.6 · 10⊃min;⊃5; mol per mole of silver for each emulsion Red-sensitive dye VII for the red-sensitive emulsion

5.1 · 10⊃min;⊃4; mol per mole of silver for each emulsion

Cyan and yellow coupler dispersions were prepared according to the procedure for preparing the coupler dispersion in Example 8.

Cyan and yellow dye dispersions were also prepared according to the method for preparing the coupler dispersion of the present invention described in Example 8. For comparison purposes, a colored dispersion product was prepared which is introduced into a layer forming a colored layer capable of being decolored during a heat development process. In this comparative colorant dispersion, the following yellow, magenta and cyan leuco dyes as well as zinc complex were introduced.

The obtained silver halide emulsions, coupler dispersions and dye dispersions were used to prepare multilayer heat-developable color photographic light-sensitive materials II-211, II-213, II-214, II-223 and II-224.

The emulsions used in the layers are shown in Table 25. Table 24 (1/5) Table 24 (2/5) Table 24 (3/5) Table 24 (4/5) Table 24 (5/5) Yellow coupler (u) Antifogging agent (w) Cyan coupler (aa) Leuco dye (ab) Development resources (v) Yellow leuco dye (x) Table 25

The photographic properties of these photosensitive materials were investigated as in Example 8. First, each of the photosensitive materials was exposed through a blue, green or red filter using an optical wedge (100 lux for 1/100 sec.).

Warm water (40ºC, 16 ml/m²) was applied to the surface of the exposed photosensitive material, and this surface was attached to the surface of the processing material II-P-1 in an opposite manner. Heat was applied thereto using a heat drum at 80ºC for 25 seconds (this period ranged from attachment to peeling off for heat treatment). No fixation was performed. After the photosensitive materials were peeled off in the development step, the samples exposed through the blue filter, the samples exposed through the green filter, and the samples exposed through the red filter showed yellow-colored wedge-shaped images, magenta-colored wedge-shaped images, and cyan-colored wedge-shaped images. The color separation properties of the green-sensitive layers and the red-sensitive layers with respect to blue light were optically determined.

In addition, the maximum density of each of these samples was determined. No fixation procedure was carried out. The results are shown in Table 26. Table 26

Table 26 shows that the present invention provides excellent effects. That is, even when the color photographic light-sensitive material used in the present invention is applied to a structure having three O layers, three M layers and three U layers (where O, M and U correspond to blue light, green light and red light which turn into yellow, magenta and cyan respectively), a high maximum density can be obtained as in Example 8. Also When a color photographic material prepared as in the present example was examined for color separation using a blue-sensitive, green-sensitive and red-sensitive layer, excellent color separation with respect to blue light was observed, confirming high quality of the products.

Claims (13)

1. A method for producing a color image comprising the steps of performing mutual adhesion between a heat-developable photosensitive material and a processing material containing a decolorizing agent or a precursor thereof in the presence of water after the heat-developable photosensitive material has been imagewise exposed or simultaneously with the imagewise exposure of the heat-developable photosensitive material; Applying heat to the adhering or bonding heat-developable, photosensitive material and processing material; and separating the heat-developable photosensitive material from the processing material, thereby obtaining a color image on the heat-developable photosensitive material and causing decolorization of the dyes; wherein the heat-developable photosensitive material comprises a support and a photosensitive layer provided on the support, wherein the heat-developable photosensitive material contains dyes which are decolored by reaction with a decolorizing agent at the time of the development process, the dyes are non-diffusible and at least a part of the decolored dyes resulting from the development process are non-diffusible. 2. The method according to claim 1, wherein the dyes have neither a carboxyl group nor a sulfo group in their molecules. 3. A method according to claim 1 or 2, wherein the heat-developable photosensitive material further contains a decolorizable dye layer formed from a dispersion in which oil droplets formed by dissolving at least one of the dyes in oil and/or an oil-soluble polymer are dispersed in a hydrophilic binder. 4. Process according to one of claims 1 to 3, wherein the dyes are represented by the following formulas (I) to (IV): A51 = L51 - (L52 = L53)m51 - Q51 (I) A51 = L51 - (L52 = L53)n51 - A52 (II) A 51 (= L51 - L52)p51 = B 51 (III) (NC)2C = C(CN) - Q51 (IV) where "=" represents a double bond and "-" represents a single bond; each of A51 and A52 represents an acidic nucleus, and B 51 represents a basic nucleus ; Q51 represents an aryl group or a heterocyclic group; each of L51, L52 and L53 represents a methine group which may have a substituent, wherein the substituents may be linked together to form a 5- or 6-membered ring; m51 represents 0,1 or 2; each of n51 and p51 represents 0,1,2 or 3; wherein when a plurality of L51, a plurality of L52 or a plurality of L53 are present in the molecule, the elements of each of L51, L52 and L53 may be identical to or different from each other; provided that the compounds represented by formulas (I) to (IV) have no carboxyl group and no sulfo group, that the compounds represented by formulas (I) to (IV) have no diffusion group, that the resulting products after a development process (decolorization) are also non-diffusible and are not substantially eluted from the photosensitive material, and that the compounds represented by formulas (I) to (IV) have no group which initiates a redox reaction during the development process and subsequently undergoes bond cleavage to divide into a plurality of molecules. 5. The process according to claim 4, wherein each of the acidic nuclei A51 and A52 is a cyclic ketomethylene compound or a compound having a methylene group arranged between two electrophilic groups. 6. The method of claim 5, wherein the cyclic ketomethylene compound is 2- pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one, or pyrrolin-2-one; wherein the compound having a methylene group disposed between electrophilic groups is a group represented by Z51-CH2-Z52, wherein each of Z51 and Z52 independently represents -CN, -SO2R51, -COR51, -COOR51, -CON(R52)2, -SO2N(R52)2, -C[=C(CN)2]R51 or -C[C(CN)2]N(R51)2; R51 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a hydrocyclic group; R52 represents a hydrogen atom or the groups indicated for R51; wherein each of R51 and R52 may have a substituent, and when there are a plurality of R51 or a plurality of R52, they may be identical to each other or different from each other. 7. The method according to any one of claims 4 to 6, wherein the basic nucleus B51 is pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzoimidazole, benzothiazole, oxazoline, naphthoxazole, or pyrrole. 8. A method according to any one of claims 1 to 7, wherein the photosensitive layer contains photosensitive halide grains. 9. The method according to claim 8, wherein the photosensitive layer contains a developing agent and a coupler. 10. A method according to any one of claims 1 to 9, wherein the photosensitive layer of the heat-developable photosensitive material contains a developing agent, and the processing layer of the processing material contains a base and/or a base precursor (which may be identical or different from the decolorizing agent or a precursor thereof), and wherein the surface the photosensitive layer of the heat-developable material adheres to the surface of the processing layer of the processing material, wherein or when water is applied to the surface of the photosensitive layer and/or the surface of the processing layer, followed by heat development. 11. A process according to any one of claims 1 to 10, wherein the dyes are contained in an amount of 0.005 to 2 mmol per m² of the heat-developable photosensitive material. 12. The method according to any one of claims 1 to 10, wherein the decolorizing agent or a precursor thereof is contained in the heat-developable light-sensitive material in an amount of 0.1 to 200 times the amount of the dyes contained. 13. A method according to any one of claims 1 to 7 and 10 to 12, wherein at least one photosensitive layer contains a binder and a compound which undergoes a coupling reaction with the photosensitive silver halide grains and an oxidation product of a developing agent to thereby form a dye, and wherein after exposure, the surface of the photosensitive layer of the heat-developable photosensitive material adheres to the surface of the processing layer of the processing material containing a decolorizing agent or a precursor thereof, followed by heat development to produce color images, the heat-developable photosensitive material being further characterized in that at least one photosensitive layer contains: i) an emulsion containing silver halide grains comprising at least 50 mol% silver chloride, wherein tabular grains with (100) major faces form at least 50% of the projected area, each grain having a rectangular projected area with an adjacent or contiguous edge ratio of 1:1 to 1:2 and an aspect ratio of at least 2 or ii) an emulsion containing silver halide grains comprising at least 50% silver chloride, wherein tabular grains having (111) major faces form at least 50% of the projected area, each grain having a hexagonal projected area with an adjacent or contiguous edge ratio of 1:1 to 1:10 and an aspect ratio of at least 2.