JP2000098557A - Silver halide photographic sensitive material containing aromatic boron derivative which releases photographically useful group, and image forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material and an image forming method showing little changes in treatment or in photographic property during storage. SOLUTION: This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on a supporting body, and contains a compd. expressed by the formula of (R)2-B-Ar-CH2-(L)n-PUG. In the image forming method, the silver halide photographic sensitive material is treated in the presence of peroxides. In the formula, each R is independently a hydroxy group, alkoxy group, aryloxy group or an aryl group, where the two R groups may form a bond with each other to form a ring, Ar is a substd. or unsubstd. aryl group or a heterocyclic group, L is a connecting group, PUG is a photographically useful group, n is an integer 0 to 3, and when R is a hydroxy group, the compd. of the formula may form a triboroxane structure by dehydration of three molecules.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel photographic recording material containing a photographic useful compound in a protected form. The present invention also relates to an image forming method in which the photographic useful compound is released imagewise or uniformly from its protective body.

Photographically useful compounds are compounds that can be used in photographic materials to obtain certain results or special effects, and include, for example, couplers, color developing agents, auxiliary developing agents, redox compounds , A dye, a development inhibitor, a development accelerator, a stabilizer, an antioxidant, a bleaching accelerator, and a fixing agent.

[0003]

2. Description of the Related Art In general, in a photographic light-sensitive material, the incorporation of a photographic useful compound necessary for forming an image in the light-sensitive material simplifies the preparation of a developing solution and facilitates the management of the developing solution. It has many advantages, such as less change in composition and easier waste liquid treatment. However, it is not easy to incorporate an air oxidation, hydrolysis, or thermally unstable photographic useful compound into a photosensitive material. For example, in a photosensitive material, an aromatic primary amine which is a color developing agent is used. Has many drawbacks, such as desensitization of the light-sensitive material, generation of fog or stain, and insufficient color development during storage, and has not yet been put to practical use.

[0004] In order to solve such a problem, a useful photographic compound is incorporated in a light-sensitive material in the form of a compound in which the compound is protected in an inactive or relatively inactive form, and the pH fluctuation during processing is utilized. Thus, methods for imparting their activity by performing deprotection during treatment have been attempted. However, a disadvantage of this method is that it is difficult to adequately control the difference in activity between the protected compound and the deprotected compound, for example, because the protection is so stable that Change does not completely deprotect,
Conversely, inadequate protection stability may result in a partial release of the active photographic useful compound under conditions during prolonged storage.

[0005] Such protecting groups include, for example, US Pat. Nos. 4,690,885 and 4,358,525.
No. 4,554,243 and 5,019,49
No. 2.

As a technique for deprotecting a protected photographically useful compound which does not have the above-mentioned drawbacks by an appropriate method, a dinucleophile having a function of selective deprotection is added to a processing solution. U.S. Pat.
No. 56,525 and JP-A-9-133990.

As a similar technique, an image forming method for performing selective deprotection in the presence of a peroxide anion is reported in US Pat. No. 5,538,834.

However, in these techniques, although the addition of a dinucleophile or a peroxide to the treatment solution promotes the deprotection at the time of treatment, it utilizes the difference in the reaction rate to hydroxide ions. Indeed, the deprotection reactions utilized can, to varying degrees, proceed with hydroxide ions alone. Therefore, it is difficult to completely achieve the above-mentioned activity at the time of treatment and storage stability completely, and the level is still insufficient.

On the other hand, the organic boron compound undergoes an oxidation reaction in an alkaline solution in the presence of a peracid or a peroxide,
Conversion to a hydroxyl group is known as one of the oxidation reaction processes of an organic synthesis reaction called a hydroboration reaction. This reaction can specifically convert a carbon-boron bond to a carbon-oxygen bond only in the presence of a peracid or peroxide, and does not proceed with hydroxide ion alone. An example of using this reaction as a protecting group for an amino acid in organic synthetic chemistry is described in Tetrahedron Letters, p. 4629 (1975). However, the application of this reaction to the release reaction of a useful group for photography is not disclosed, and it is not at all possible whether or not the above-mentioned processing activity and storage stability can be compatible in a complicated photosensitive material. It was unpredictable.

It is an object of the present invention to provide a photographic material and an image forming method which have little fluctuation in processing and photographic properties during storage.

[0011]

The above objects have been attained by the present invention described below. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, characterized by containing a compound represented by the following general formula (1).

General formula (1) (R) ₂ B-Ar-CH _2- (L) _n -PUG In general formula (1), each R is independently a hydroxyl group,
Represents an alkoxy group, an aryloxy group and an aryl group. Two Rs may combine with each other to form a ring. A
r represents a substituted or unsubstituted aryl group or heterocyclic group, and L represents a linking group. PUG represents a photographic useful group, and n represents an integer of 0 to 3. When R is a hydroxyl group,
The compound of the general formula (1) may have a triboroxane structure by a dehydration reaction between three molecules.

The image forming method of the present invention is characterized in that the above-mentioned silver halide photographic material is processed in the presence of a peroxide.

Next, the compound represented by formula (1) will be described in detail.

In the general formula (1), the Ar group is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. The aryl group preferably has 6 to 30 carbon atoms, and specific examples include a phenyl group and a naphthyl group. Further, the heterocyclic group is preferably a 3- to 8-membered ring having at least one oxygen atom, nitrogen atom or sulfur atom as a hetero atom in a ring-constituting atom, and condensed with another aromatic ring. And specific examples thereof include a 2-pyridyl group, a 2-furyl group, a 2-benzoxazolyl group, and a 2-thienyl group. Particularly preferred as Ar is an aryl group.

In the general formula (1), when the Ar group has a substituent, specific examples thereof include a linear or branched alkyl group having 1 to 60 carbon atoms (for example, methyl group,
Ethyl group, propyl group, isopropyl group, t-butyl group, 2-ethylhexyl group, nonyl group, undecyl group,
A pentadecyl group, an n-hexadecyl group, a 3-decaneamidopropyl group, etc.), a cycloalkyl group having 3 to 60 carbon atoms (eg, a cyclopropyl group, a 1-ethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.), a carbon number of 6 To 30 aryl groups (e.g., phenyl group, naphthyl group, etc.) and a heterocyclic group having 2 to 60 carbon atoms (a hetero atom having at least one oxygen atom, nitrogen atom or sulfur atom, An 8-membered monocyclic or condensed ring, such as a 2-pyridyl group, a 2-furyl group, a 2-benzoxazolyl group, or a 2-thienyl group), an acylamino group having 2 to 60 carbon atoms {eg, acetylamino Group, n-butanoylamino group, octanoylamino group, 2-hexadecanoylamino group, 2- (2 ', 4'-di-t-amylphenoxy) butano Arylamino group, benzoylamino group,
Nicotinoylamino group and the like; and other amino groups having 0 to 60 carbon atoms (for example, unsubstituted amino group, monoalkylamino group, dialkylamino group, arylamino group, alkylarylamino group, specifically, unsubstituted Amino group, diethylamino group, n-octylamino group, 3- (2 ′,
4'-di-t-amylphenoxy) propylamino group,
A morpholino group, etc.), an alkoxy group having 1 to 60 carbon atoms (e.g., methoxy group, ethoxy group, butoxy group, n-octyloxy group, hexadecyloxy group, 2-methoxyethoxy group, etc.), Aryloxy group (for example, phenoxy group, 2,4-t-amylphenoxy group,
4-t-butylphenoxy group, naphthoxy group, etc.), an alkylthio group having 1 to 60 carbon atoms (for example, methylthio group,
An ethylthio group, a butylthio group, a hexadecylthio group, etc.), an arylthio group having 6 to 60 carbon atoms (eg, a phenylthio group, a 4-dodecyloxyphenylthio group, etc.),
An acyl group having 1 to 60 carbon atoms (eg, acetyl group, benzoyl group, butanoyl group, dodecanoyl group, etc.), an acyloxy group having 6 to 60 carbon atoms (eg, benzoyloxy group, octanoyloxy group, 2-hexadecanoyl) Oxy group, 2- (2 ', 4'-di-t-amylphenoxy)
A sulfonyl group having 1 to 60 carbon atoms (e.g., methanesulfonyl group, butanesulfonyl group, toluenesulfonyl group, etc.), a sulfonylamino group having 1 to 60 carbon atoms (e.g., methanesulfonylamino group,
Phenylsulfonylamino group), cyano group, carbon number 2
To 60 alkoxycarbonyl groups (e.g., ethoxycarbonyl group, hexyloxycarbonyl group, dodecyloxycarbonyl group, etc.), and aryloxycarbonyl groups having 7 to 30 carbon atoms (e.g., phenoxycarbonyl group,
A carbamoyl group having 1 to 60 carbon atoms (eg, N, N-dicyclohexylcarbamoyl group), or a sulfamoyl group having 0 to 60 carbon atoms (eg, N, N-dimethylsulfamoyl group) ), A carboxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) and a hydroxyl group.

Among these substituents, preferred are an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonylamino group and a hydroxyl group, and more preferred are an alkoxy group, an acylamino group and a sulfonyl group. An amino group and a hydroxyl group are preferred, and particularly preferred groups include an alkoxy group and a hydroxyl group.

If possible, these substituents may be linked to each other to form a ring, and examples thereof include a cyclopentene ring, a cyclohexane ring, a norbornene ring, and a dihydrofuran ring.

In addition, these substituents, if possible,
It may further have a substituent, and as the substituent, the substituents listed as the substituent on the Ar group can be applied,
Preferably, an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, a cyano group, a carboxyl group, or a hydroxyl group, and particularly preferably an alkyl group Group, alkoxy group, hydroxyl group and carboxyl group.

It is preferred that at least one of the substituents on the Ar group incorporates a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a photographically inert group having 8 or more carbon atoms, such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amide group, a ureido group, a sulfonamide group, an ester group, and a sulfonyl group. Group,
It can be selected from those comprising an acyl group or the like and a combination of these groups or a group such as a hydroxyl group.

In the general formula (1), -CH _2- (L)
_When the Ar group is an aryl ring, the bonding position of Ar in _n- PUG is ortho or para to the boron atom. When it is the 2-position or 4-position, it is in a positional relationship on the Ar group such that after the boron atom is converted to a hydroxyl group, a photographic useful group (PUG) can be released by electron transfer.

In the general formula (1), L represents a linking group, and includes a known time adjusting group (timing group), for example, described in DE-A-2803145.

[0023]

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Groups are mentioned. In this group, (-
O) A compound which releases an atom ((R) ₂ B-Ar-CH _2- )
And the carbon atom is attached to a heteroatom in the photographically useful group (PUG), linking the releasing compound with the photographically useful group. Further, when released from a photographic useful group protecting compound of the general formula (1) as described in DE-A-2855697, the compound undergoes an intramolecular nucleophilic reaction to release a photographic useful group. Group, furthermore DE-A-310502
No. 6, groups released from a photographic useful group-protecting compound represented by the general formula (1), electron transfer takes place along a conjugated system, and leads to release of a photographic useful group. And the like.

L, when released from the compound of the general formula (1), itself participates in a coupling reaction or a redox reaction, and reacts with a nucleophile released imagewise as a result of the reaction. A group capable of imagewise releasing PPG by a coupling reaction or an imagewise redox reaction with silver halide may be used.

In the general formula (1), -CH _2- (L) _n-
The PUG is in a positional relationship on Ar such that after the boron atom is converted to a hydroxyl group, a photographically useful group can be released by electron transfer along a conjugated system.

In the general formula (1), PUG represents a photographically useful group. These groups include, for example, halogen ions (chloride ions, bromide ions, iodide ions) or couplers, developing agents, auxiliary developing agents, redox compounds, dyes, development inhibitors, development accelerators, stabilizers,
Compounds selected from antioxidants, bleaching accelerators, and fixing agents are exemplified. In formula (1), a color developing agent is particularly preferred as PUG.

When R is a hydroxyl group, the compound of the general formula (1) may have a triboroxane structure formed by a dehydration reaction between three molecules depending on its existence conditions. And are in an equilibrium state, and exhibit basically the same action.

Preferred compounds among the compounds represented by the general formula (1) are represented by the following general formula (2).

[0030]

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In the general formula (2), R ¹ each independently represents a hydroxyl group, an alkoxy group, an aryloxy group or an aryl group. Two R ^{1 s} may combine with each other to form a ring. R ² represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
Represents an acylamino group, a sulfonylamino group or a substituted amino group, or a hydroxyl group. A plurality of R ² may combine with each other to form a ring. CH ₂ represents a methylene group located at the ortho or para position of the boron atom, and L represents a linking group. P
UG represents a photographic useful group, and m represents an integer of 1 to 4. When m is 2 or more, a plurality of R ² may be the same or different. p represents an integer of 0 to 2. When R ¹ is a hydroxyl group, the compound of the general formula (2) may have a triboroxane structure by a dehydration reaction between three molecules.

As the groups represented by R ¹ and R ² in the general formula (2), those included in the substituents listed for the substituent on Ar in the general formula (1) can be applied. R ¹ is preferably a hydroxyl group or an alkoxy group, particularly preferably a hydroxyl group.

R ² is preferably a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, a sulfonylamino group,
More preferred groups are a hydroxyl group, an alkyl group, an alkoxy group, an amino group, and an acylamino group, and a hydroxyl group and an alkoxy group are particularly preferred. p is preferably 0 or 1.

Among the compounds represented by the general formula (2), more preferred compounds are represented by the general formula (3).

[0035]

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In the general formula (3), R ³ independently represents a hydroxyl group, an alkoxy group or an aryloxy group;
R ⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, alkoxy group, acylamino group, sulfonylamino group, or hydroxyl group. Multiple R ³
May combine with each other to form a ring. CH ₂ represents a methylene group located at the ortho or para position of the boron atom. PUG represents a photographic useful group, and r represents an integer of 1 to 4. When r is 2 or more, a plurality of R ⁴ may be the same or different. When R ³ is a hydroxyl group, the compound of the general formula (3) may have a triboroxane structure by a dehydration reaction between three molecules.

As the group represented by R ⁴ in the general formula (3), those included in the substituents listed for the substituent on Ar in the general formula (1) can be applied. R ⁴ is preferably a hydroxy group, an alkyl group, an alkoxy group, an acylamino group, or a sulfonylamino group, and a hydroxy group and an alkoxy group are particularly preferred. R ³ is preferably an alkoxy group or a hydroxyl group, and particularly preferably a hydroxyl group.

Among the compounds represented by the general formula (3), more preferred compounds are represented by the general formula (4).

[0039]

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In the general formula (4), R ⁵ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an acylamino group, a sulfonylamino group, or a hydroxyl group. A plurality of R ⁵ may combine with each other to form a ring. CH ₂ represents a methylene group located at the ortho or para position of the boron atom. PUG represents a photographic useful group, and q represents an integer of 1 to 4. When q is 2 or more, a plurality of R ⁵ may be the same or different.
The compound of the general formula (4) may have a triboroxane structure by a dehydration reaction between three molecules.

In the general formula (4), as the group represented by R ⁴ , those included in the substituents listed for the substituent on Ar in the general formula (1) can be applied. R ⁴ is preferably a hydroxy group, an alkyl group, an alkoxy group, an acylamino group,
It is a sulfonylamino group, and a hydroxy group and an alkoxy group are particularly preferred.

Specific examples of the compound included in the general formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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These compounds can be synthesized by the method described below or a method analogous thereto. A typical synthesis example of the compound of the present invention is shown below. Other compounds can be synthesized by the same method and a method analogous thereto.

The exemplified compound (1) was synthesized as follows.

[0052]

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Compound (A): n was added to a solution of p-bromobenzyl alcohol (30 mmol) in THF (300 ml).
-Butyl lithium (2.5 M hexane solution, 26 ml)
Was added at -78 ° C and stirred for 30 minutes. Further -78 ° C
Then, trimethyl borate (9.4 g, 90 mmol) was added thereto, and the mixture was stirred for 30 minutes, and then slowly heated to room temperature.
To the reaction solution, 60 ml of a 10% aqueous sodium hydroxide solution was added, and after stirring for 1 hour, concentrated hydrochloric acid was added until pH = 4. After extracting the reaction solution with ethyl acetate according to a conventional method,
The extract is concentrated, and the residue is purified by silica gel column chromatography (n
-Hexane / ethyl acetate) to obtain a compound (A) (2.7 g, yield 60%).

Compound (1): Toluene 5 of compound (A)
To 0 ml of the solution, 1.1 g of catechol was added, and the mixture was refluxed for 3 hours while removing water. Next, the reaction solution was concentrated, 10 ml of acetonitrile was added thereto, and the compound (B) was further added.
2.1 g and 0.9 ml of triethylamine were added,
For 4 hours. The reaction solution was cooled to room temperature, added to dilute aqueous hydrochloric acid, and extracted with ethyl acetate according to a conventional method. The extract was concentrated, and the residue was purified by silica gel column chromatography (n-hexane / ethyl acetate) to obtain compound (1) (yield 2.0 g).

Next, the light-sensitive material containing the compound of the present invention will be described in detail. When the compound of the present invention is added to a light-sensitive material, the compound represented by the general formula (1)
When no suitable peroxide or peracid is present, that is, it is difficult to release a photographically useful group only with a mere alkaline solution. Suitable peroxides are, for example, compounds of the formula

ROOH RCOOOH (wherein R is a hydrogen atom, a substituted or unsubstituted alkyl group,
An aryl group. ) When the peroxide represented by the above formula is added to, for example, an image forming processing solution, the protected photographically useful group represented by the general formula (1) is converted into an appropriate peroxide in the processing solution during processing. It reacts with oxides to quickly release photographically useful groups and exhibit its specific activity.

The following are examples of suitable peroxides.

[0058]

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When the compound represented by the general formula (1) of the present invention is added to a light-sensitive material, a protective layer, a light-sensitive silver halide emulsion layer, a non-light-sensitive fine grain silver halide in the light-sensitive material are used. It can be contained in at least one of an emulsion layer, an intermediate layer, a filter layer, an undercoat layer, an antihalation layer and the like, but is preferably used in a photosensitive emulsion layer. The compounds represented by general formula (1) of the present invention may be used in combination of two or more kinds.

The amount of peroxide added in the processing solution is
It is preferably from 0.1 mmol / liter to 1 mol / liter, and more preferably from 0.1 mmol / liter.
0.5 mo1 / liter.

Next, among the compounds represented by the general formula (1), the photosensitive compound of the present invention applied when PUG is a compound which is a color developing agent (hereinafter, this compound is abbreviated as a color developing agent precursor). The material will be described.

The couplers preferably used in the present invention include compounds having the structures represented by the following formulas (8) to (19). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0063]

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Formulas (8) to (11) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas (8) to (10), R ¹⁵ is an optionally substituted alkyl group, aryl group or heterocyclic residue. In the general formula (11), R ¹⁶ is an aryl group or a heterocyclic residue which may have a substituent.

The substituent which R ¹⁴ , R ¹⁵ and R ¹⁶ may have represents a hydrogen atom or a substituent. Here, examples of the substituent include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, trifluoromethyl,
Methyl, ethyl, propyl, heptafluoropropyl,
Isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl and the like, a linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms (for example, vinyl,
1-methylvinyl, cyclohexen-1-yl and the like, an alkynyl group having a total of 2 to 50 carbon atoms (for example, ethynyl,
-Propynyl, etc.), an aryl group having 6 to 50 carbon atoms (eg, phenyl, naphthyl, anthryl, etc.),
50 acyloxy groups (eg, acetoxy, tetradecanoyloxy, benzoyloxy, etc.), having 1 to 5 carbon atoms
0 carbamoyloxy group (for example, N, N-dimethylcarbamoyloxy and the like), a carbonamide group having 1 to 50 carbon atoms (for example, formamide, N-methylacetamide, acetamide, N-methylformamide, benzamide and the like), carbon Number 1 to 50 sulfonamide groups (for example, methanesulfonamide, dodecanesulfonamide,
Benzenesulfonamide, p-toluenesulfonamide, etc.), a carbamoyl group having 1 to 50 carbon atoms (for example, N-
Methylcarbamoyl, N, N-diethylcarbamoyl,
N-mesylcarbamoyl and the like, a sulfamoyl group having 0 to 50 carbon atoms (for example, N-butylsulfamoyl, N,
N-diethylsulfamoyl, N-methyl-N- (4-
Methoxyphenyl) sulfamoyl etc.), having 1 to 5 carbon atoms
An alkoxy group of 0 (for example, methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy,
Dodecyloxy, 2- (2,4-di-t-pentylphenoxy) ethoxy, etc.), an aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4-methoxyphenoxy,
Naphthoxy, etc.), an aryloxycarbonyl group having 7 to 50 carbon atoms (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.), an alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), carbon number 1 to 50 N-acylsulfamoyl groups (for example, N-tetradecanoylsulfamoyl,
N-benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (e.g., methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl,
-Hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (for example, benzenesulfonyl, p
-Toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl and the like), an alkoxycarbonylamino group having 2 to 50 carbon atoms (such as ethoxycarbonylamino), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (such as phenoxycarbonylamino, Naphthoxycarbonylamino), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, mercapto group Etc.), an alkylsulfinyl group having 1 to 50 carbon atoms (e.g., methanesulfinyl, octanesulfinyl, etc.), an arylsulfinyl group having 6 to 50 carbon atoms (e.g., benzenesulfinyl, 4-chlorophenylsulfinyl, p Toluene sulfinyl, etc.),
An alkylthio group having 1 to 50 carbon atoms (for example, methylthio, octylthio, cyclohexylthio, etc.), a carbon number of 6
To 50 arylthio groups (e.g., phenylthio, naphthylthio, etc.) and a ureido group having 1 to 50 carbon atoms (e.g.,
3-methylureide, 3,3-dimethylureide, 1,
A 3- to 12-membered monocyclic or condensed ring containing at least one heteroatom such as nitrogen, oxygen and sulfur; , 2-furyl, 2-pyranyl,
2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-
Benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (e.g., acetyl, benzoyl, trifluoroacetyl, etc.), a sulfamoylamino group having 0 to 50 carbon atoms (e.g., N-butylsulfur) Famoylamino, N-phenylsulfamoylamino, etc.), a silyl group having 3 to 50 carbon atoms (for example, trimethylsilyl,
Dimethyl-t-butylsilyl, triphenylsilyl, etc.), a halogen atom (for example, a fluorine atom, a chlorine atom,
Bromine atom). The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

These substituents may combine with each other to form a condensed ring. The condensed ring is preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring. The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 34 or less. Also, one or more is preferable.

In the general formulas (8) to (11), Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized form of a color developing agent. Examples of Y include a heterocyclic group (a heterocyclic atom is a saturated or unsaturated monocyclic or condensed 5- to 7-membered ring containing at least one nitrogen, oxygen, sulfur or the like, and examples thereof include succinimide and maleic Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidin-2,4-dione , Thiazolidine-2,4-dione, imidazolidine-2-one, oxazolin-2-one, thiazoline-2
-One, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-
Pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine,
Parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone,
6-pyridazone, 2-pyrazone, 2-amino-1,3,
4-thiazolidine, 2-imino-1,3,4-thiazolidine-4-one, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), aryloxy group (eg, phenoxy, 1-naphthoxy, etc.), hetero A ring oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), an acyloxy group (eg, acetoxy, benzoyloxy, etc.),
Alkoxy group (eg, methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.), alkoxycarbonyloxy group (Eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4- Oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy group (eg, methanesulfonyloxy, etc.), arylsulfonyloxy Si group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide group (eg, acetamide, trifluoroacetamide, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl group ( For example, methanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl), alkylsulfinyl group (eg, methanesulfinyl), arylsulfinyl group (eg, benzenesulfinyl), arylazo group (eg, phenylazo, naphthylazo) Carbamoylamino group (for example, N-methylcarbamoylamino and the like).

Y may be substituted by a substituent,
Examples of the substituent for substituting Y include those described as the substituent for R ¹⁴ , R ¹⁵ and R ¹⁶ . Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group.

In the general formulas (8) to (11), R ¹⁴ and R ¹⁵ and R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring.

Formula (12) represents a coupler referred to as a 5-pyrazolone coupler, wherein R ¹⁷ is an alkyl group,
Represents an aryl group, an acyl group or a carbamoyl group. R
¹⁸ represents a phenyl group or a phenyl group substituted by one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups or acylamino groups.
Among the 5-pyrazolone couplers represented by the general formula (12), those in which R ¹⁷ is an aryl group or an acyl group, and R ¹⁸ is a phenyl group substituted by one or more halogen atoms are preferable.

To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecanamidophenyl group, a 2-chloro-5- (3-octadecenyl) group. -1-succinimide) phenyl group, 2-chloro-5-
An aryl group such as an octadecylsulfonamidophenyl group or a 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group or an acetyl group, 2- (2,4-di-t) -Pentylphenoxy) butanoyl group, benzoyl group, 3- (2,
Acyl groups such as 4-di-t-amylphenoxyacetamido) benzoyl group, and these groups may further have a substituent, and these are organic groups linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a substituent or a halogen atom. Y has the same meaning as described above.

R ¹⁸ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group.

The general formula (13) represents a coupler called a pyrazoloazole coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ contains 2 to 4 nitrogen atoms 5
Represents a group of nonmetallic atoms necessary for forming a membered azole ring, and the azole ring may have a substituent (including a condensed ring).

Among the pyrazoloazole-based couplers represented by the general formula (13), imidazo [1,2-b] described in US Pat. No. 4,500,630 is preferred in view of the spectral absorption characteristics of the coloring dye. Pyrazoles, U.S. Pat. No. 4,500,
No. 654, pyrazolo [1,5-b] -1,2,4
-Triazoles and pyrazolo [5,1-c] -1,2,4-triazoles described in U.S. Pat. No. 3,725,067 are preferred.

For details of the substituents on the azole ring represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 201443 is a pyrazolotriazole coupler having a carboxamide group in the molecule. Y has the same meaning as described above.

Formulas (14) and (15) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ²⁰ is a hydrogen atom or —CONR
_{^{22 R 23, -SO 2 NR 22}} R 23, -NHCOR 22, -NH
CONR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent.
In the general formulas (14) and (15), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. Examples of the substituent of R ^{21 to} R ²³ include those described as examples of the substituent of R ¹⁴ , R ¹⁵ and R ^{16 in} the general formulas (8) to (10). Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (14) include US Pat. No. 2,369,
No. 929, No. 2,801,171, No. 2,77
No. 2,162, No. 2,895,826, No. 3,7
72-002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729,
9,166,956 and the like, U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427. , 767, and the like. Y is the same as described above.

Preferred examples of the naphthol coupler represented by the general formula (15) include US Pat. No. 2,474,2.
No. 93, 4,052, 212, 4,146
No. 396, No. 4,282,233, No. 4,29
Examples thereof include 2-carbamoyl-1-naphthols described in US Pat. No. 6,200 and the like and 2-carbamoyl-5-amido-1-naphthols described in U.S. Pat. No. 4,690,889. Y is the same as described above.

Formulas (16) to (19) are couplers called pyrrolotriazoles, and R ³² , R ³³ and R ³⁴ represent a hydrogen atom or a substituent. Y is as described above. Examples of the substituent for R ³² , R ³³ , and R ³⁴ include those described above as examples of the substituent for R ¹⁴ , R ¹⁵ , and R ¹⁶ . Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (16) to (19) include European Patent Nos. 488,248A1 and 491,197A1.
No. 545,300, a coupler wherein at least one of R ³² and R ³³ is an electron-withdrawing group. Y is the same as described above.

Others, fused phenol, imidazole,
Couplers having a structure such as pyrrole, 3-hydroxypyridine, active methylene other than the above, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle can be used.
As the fused phenol coupler, US Pat. No. 4,32
No. 7,173, No. 4,564,586, No. 4,9
The couplers described in JP-A No. 04,575 and the like can be used. As the imidazole coupler, US Pat. No. 4,818,
Nos. 672 and 5,051,347 can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used. Active methylene and active methine couplers are described in US Pat. Nos. 5,104,783 and 5,16.
The couplers described in 2,196 and the like can be used. 5,5
-As a fused heterocyclic coupler, US Pat.
Pyrrolopyrazole couplers described in JP-A-4,289, and pyrroleimidazole couplers described in JP-A-4-174429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585 and JP-A-4-20473.
No. 0, pyrrolotriazine couplers described in EP-A-556700, and the like can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used. Specific examples of the coupler that can be used in the present invention are shown below, but the present invention is not limited thereto.

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The coupler of the present invention may be added to any layer, but it is preferable to add the coupler to a layer containing a silver halide emulsion. It is preferable that the silver halide is added so as to have a complementary color relationship with the color of light to which the silver halide is exposed. For example, a layer containing a blue-sensitive silver halide emulsion preferably contains a yellow coupler, and a layer containing a green-sensitive silver halide emulsion contains a magenta coupler. Preferably, a cyan coupler is added to the layer containing the red-sensitive silver halide emulsion. However, when the photosensitive material of the present invention is subjected to laser exposure, it is not important to add a coupler because of the relationship between the color sensitive to silver halide and the complementary color as described above. A yellow coupler, a magenta coupler in a layer containing a red-sensitive silver halide emulsion, a cyan coupler in a layer containing an infrared-sensitive silver halide emulsion, and so on. You may add so that it may not be a complementary color relationship.

As a yellow coupler, an active methylene type coupler is preferably used. As the magenta coupler, a pyrazolone-type or pyrazoloazole-type coupler is preferably used, and in particular, a pyrazoloazole-type coupler is preferably used. As the cyan coupler, a phenol coupler, a naphthol coupler, and a pyrrolotriazole coupler are preferably used, and particularly, a phenol coupler and a pyrrolotriazole coupler are preferably used.

The color developing agent precursor according to the present invention is used in an amount of 0.01 mmol per one color forming layer in order to obtain a sufficient color forming density.
/ M ^{2 to} 10 mmol / m ² .
A more preferred usage amount is 0.05 mmo1 / m ^{2 to 5} mm
o1 / m ² , and a particularly preferred usage amount is 0.1 mmo1.
/ M ^{2 to 1} mmo1 / m ² . This range is preferred in that a sufficient color density can be obtained.

The amount of the coupler in the color forming layer in which the color developing agent precursor of the present invention is used is preferably 0.05 to 20 times, more preferably 0.1 to 20 times the molar amount of the color developing agent precursor. Times to 10 times, particularly preferably 0.2 to 5 times
It is twice. This range is preferable in that a sufficient color density can be obtained.

The color light-sensitive material of the present invention is basically obtained by coating a support with a photographic constituent layer comprising at least one hydrophilic colloid layer, and any of the photographic constituent layers is provided with a photosensitive silver halide. , A dye-forming coupler, and a color developing agent precursor.

In the most typical embodiment, the dye-forming coupler and the color developing agent precursor used in the present invention are added to the same layer. Can be. These components are preferably added to a silver halide emulsion layer or a layer adjacent to the silver halide emulsion layer in the light-sensitive material, and particularly preferably added to a silver halide emulsion layer.

The color developing agent precursor and the coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), and emulsified in an aqueous gelatin solution. An oil-in-water dispersion method of dispersing and adding to a silver halide emulsion is preferred. The high boiling organic solvent that can be used in the present invention has a melting point of 100 ° C. or less and a boiling point of 14 ° C.
Any compound that is immiscible with water at 0 ° C. or higher and is a good solvent for the color developing agent precursor and coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. In the present invention, when a high boiling organic solvent is used, the amount of the high boiling organic solvent used may be any amount, but preferably, the high boiling organic solvent / color developing agent is used in a weight ratio to the color developing agent precursor. The reducing agent ratio for use is preferably 20 or less, more preferably 0.02 to 5, and particularly preferably 0.2 to 4.

In the present invention, a known polymer dispersion method may be used. Steps of the latex dispersion method as one of the polymer dispersion methods, effects, specific examples of latex for impregnation,
U.S. Pat. No. 4,199,363, West German Patent Application No. (OL
S) No. 2,541,274, No. 2,541,230
No. JP-B-53-41091 and European Patent Publication No. 0
No. 29104, etc., and a dispersion method using a water-insoluble and organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

The average particle size of the lipophilic fine particles containing the color developing agent precursor of the present invention may be any particle size. The thickness is preferably 0.05 to 0.3 μm from the viewpoint of color development. Further, the thickness is more preferably 0.05 μm to 0.2 μm.

In general, in order to reduce the average particle size of the lipophilic fine particles, it is necessary to select the type of surfactant, increase the amount of the surfactant used, increase the viscosity of the hydrophilic colloid solution, This can be achieved by lowering the viscosity of the organic phase by using a low-boiling organic solvent in combination, or by increasing the shearing force such as increasing the rotation of the stirring blades of the emulsifier, or by lengthening the emulsification time.

The particle size of the lipophilic fine particles can be measured by, for example, an apparatus such as Nanosizer manufactured by Coulter, UK.

The light-sensitive material of the present invention contains an auxiliary developing agent or a precursor thereof since addition of the auxiliary developing agent or a precursor thereof can increase the sensitivity and accelerate the initial development. Is preferred.

The auxiliary developing agent used in the present invention is preferably pyrazolidones, dihydroxybenzenes, reductones or aminophenols, and particularly preferably pyrazolidones. The diffusivity of these compounds in the hydrophilic colloid layer is preferably low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0% or less. 0.01% or less. The precursor of the auxiliary developing agent used in the present invention is a compound which is stably present in the light-sensitive material, but which releases the above-mentioned auxiliary developing agent quickly once it is processed with a processing solution. In this case, it is preferable that the diffusivity in the hydrophilic colloid layer is low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less.
It is as follows. The solubility of the auxiliary developing agent released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility.

The auxiliary developing agent precursor of the present invention is preferably represented by the following general formula (A).

Formula (A) A- (L) _n -PUG A represents a block group in which the bond to (L) _n -PUG is cleaved during development processing, and L represents L and A in formula (A). Represents a linking group in which the bond between L and PUG is cleaved after the bond is cleaved, n represents an integer of 0 to 3, and PUG represents an auxiliary developing agent. As the auxiliary developing agent, an electron-emitting compound according to the Kendall-Peltz rule other than the p-phenylenediamine compounds is used, and the above-mentioned pyrazolidones are preferably used.

As the blocking group represented by A, the following known ones can be applied. That is, US Pat.
No. 1,476, etc., a blocking group such as an acyl group and a sulfonyl group, a blocking group utilizing a reverse Michael reaction described in JP-A-59-105542, and the like;
No. 40 or the like, a block group utilizing quinone methide or a compound similar to quinone methide by intramolecular electron transfer,
JP-A-63-318555 (European Patent Publication No. 02957)
No. 29) and the like, a blocking group using an intramolecular nucleophilic substitution reaction and a blocking group using a nucleophilic agent addition reaction to a conjugated unsaturated bond described in JP-A-4-186344 and the like. 62-163051, a blocking group utilizing a β-elimination reaction, JP-A-61-188540, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes, and JP-A-62-187850. A block group utilizing the Rossen rearrangement reaction of JP-A-62-147457.
Group having a reaction between an N-acyl compound of thiazolidine-2-thione and an amine and an amine having two electrophilic groups described in WO 93/03419. And a blocking group which reacts with the agent. The group represented by L is a linking group capable of cleaving (L) _n-1 -PUG after leaving from the group represented by A during development processing. Absent.

Specific examples of the auxiliary developing agent or its precursor are shown below, but the compounds used in the present invention are not limited to these specific examples.

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These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer and the protective layer. When the compound contains an auxiliary developing agent, it is preferably used by adding it to the non-photosensitive layer.

These compounds can be incorporated into the photosensitive material by dissolving them in a water-miscible organic solvent such as methanol and adding them directly to a hydrophilic colloid layer, or by adding a surfactant to an aqueous solution or colloid. A method of adding as a dispersion, a method of dissolving in a solvent or oil substantially immiscible with water, a method of adding a substance dispersed in water or a hydrophilic colloid, or a method of adding in a state of solid fine particle dispersion Therefore, conventional known methods can be applied alone or in combination. The method for preparing the solid fine particle dispersion is described in detail in page 20 of JP-A-2-23544. The amount added to the light-sensitive material is from 1 mol% to 200 mol%, preferably from 5 mol% to 10 mol%, based on the color developing agent precursor.
0 mol%, more preferably 10 mol% to 50 mol%.

The support used in the present invention includes glass,
Any support such as paper and plastic film which can be coated with a photographic emulsion layer can be used as long as it is a transmission or reflection support. As the plastic film used in the present invention, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film, a polystyrene film and the like can be used.

The "reflective support" which can be used in the present invention means a material which enhances reflectivity to sharpen a dye image formed on a silver halide emulsion layer. Is a substrate coated with a hydrophobic resin such as titanium oxide, zinc oxide, calcium oxide, calcium sulfate and other light-reflecting substances, and a benzoxazole-based, coumarin-based, pyrazoline-based, etc. And those in which a hydrophobic resin itself containing a light-reflective substance dispersed therein is used as a support. For example, polyethylene-coated paper, polyester-coated paper, polypropylene-based synthetic paper, supports provided with a reflective layer or combined with a reflective substance, for example, glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide films , Polycarbonate film, polystyrene film, and vinyl chloride resin. With regard to polyester-coated paper, in particular European Patent EP 0,507,48
Polyester-coated paper containing polyethylene terephthalate as a main component described in No. 9 is preferably used.

The reflective support used in the present invention is preferably a paper support coated on both sides with a waterproof resin layer, wherein at least one of the waterproof resins contains fine white pigment particles. The white pigment particles are preferably contained at a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflective white pigment, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable that the surface of the pigment particles is treated with a divalent to tetravalent alcohol.

In the present invention, a support having a second-class diffuse reflective surface can be preferably used. The second type diffuse reflectivity refers to diffuse reflectivity obtained by imparting irregularities to a surface having a mirror surface and dividing the mirror surface into minute mirror surfaces facing different directions. The unevenness of the surface of the second type diffuse reflection has a three-dimensional average roughness with respect to the center plane of 0.1 to 2 μm, preferably 0.1 to 2 μm.
1.2 μm. Details of such a support are described in JP-A-2-239244.

The light-sensitive material can be provided with a photographic component layer comprising the above-described light-sensitive layer and various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer, and a back layer. Further, various filter dyes can be added to the photographic component layer in order to improve color separation.

As the binder or protective colloid that can be used in the light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. The calcium content of the gelatin is preferably 800 ppm or less,
The content of iron is preferably not more than 5 ppm, more preferably not more than 3 ppm, more preferably not more than 200 ppm. In order to prevent various fungi and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a fungicide as described in JP-A-63-271247.

The silver halide grains used in the present invention include silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide,
It is silver chloroiodobromide. Other silver salts, such as rodin silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are desired, so-called high silver chloride grains having a silver chloride content of 90 mol% or more are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material.

The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in a layered or non-layered form inside and / or on the surface of silver halide grains. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and is preferably 20 mol%.
Is more preferable. The silver bromide content of the localized layer of silver bromide is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis”, Maruzen) or the like. can do. And these localized phases can be on the inside of the particle, on the edge, corner or surface of the particle surface, but as one preferred example,
One obtained by epitaxial growth at the corner of a particle can be mentioned.

It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, the silver chloride content is 98
Emulsions of substantially pure silver chloride, such as from about mol% to about 100 mol%, are also preferably used.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in the grains. A typical example is JP-B-43-131.
No. 62, JP-A-61-215540 and JP-A-60-2
No. 22845, JP-A-60-143331, JP-A-6-143331
No. 1-75337 and JP-A-60-222844.

In order to provide a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called junction structure can be produced. These examples are disclosed in
-133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.

In the case of a joint structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, can be combined with silver halide to form a joint structure.

In the case of silver iodobromide grains having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment.

In the case of silver halide grains in which two or more silver halides exist as mixed crystals or have a structure, it is important to control the distribution of the halogen composition between the grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. Particularly, an emulsion having a high uniformity with a variation coefficient of the halogen composition distribution of 20% or less is preferable.

It is important to control the halogen composition near the surface of the grains. Increase the silver iodide content near the surface,
Alternatively, increasing the silver chloride content can be selected according to the purpose because the adsorption property of the dye and the developing speed are changed.

Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, they can be edited by the Photographic Society of Japan, “Basics of the Photographic Industry, Silver Salt Photography” (Corona), p. 163 (Showa 54) Example, two parallel twin planes
It can be selected and used according to the purpose from parallel multiple twins including two or more non-parallel twins including two or more non-parallel twin planes. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964. In the case of a normal crystal, a cube consisting of (100) planes, (111)
Octahedral particles composed of planes and dodecahedral particles composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. Further Jour
nal of Imaging Science, Vol. 30, p. 247 (1986)
) Can be selected and used according to the purpose. (100)
A tetrahedral particle in which the plane and the (111) plane coexist in one particle, a particle in which the (100) plane and the (110) plane coexist, or a particle in which the (111) plane and the (110) plane coexist,
Particles in which two faces or many faces coexist can be selected and used according to the purpose.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio greater than 1 can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Practice (1
Gatoff, Photographic Science and Engineering (Gutoff, Photograp)
hic Science and Engineering), Vol. 14, 248-2
57 (1970); U.S. Patent No. 4,434,226
Nos. 4,414,310 and 4,433,048
No. 4,439,520 and British Patent No. 2,11.
2,157 and the like. When tabular grains are used, the covering power increases,
The sensitizing dye has advantages such as an increase in color sensitization efficiency, and is described in detail in U.S. Pat. No. 4,434,226 cited above. The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. The shape of the tabular grains can be selected from triangles, hexagons, and circles. A regular hexagon having approximately equal lengths of six sides as described in U.S. Pat. No. 4,797,354 is a preferred form. Although the equivalent circle diameter of the projected area is often used as the grain size of the tabular grains, grains having an average diameter of 0.6 μm or less as described in US Pat. preferable. U.S. Pat.
Emulsions having a narrow grain size distribution as described in US Pat. No. 5,617 are also preferred. It is preferable that the thickness of the tabular grains be 0.5 μm or less, more preferably 0.3 μm or less, in terms of enhancing sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable.

It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, or to introduce them all over the grains, or to introduce them only into specific portions of the grains, for example, And the introduction of dislocations only in the fringe portion of. The introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of normal crystal grains or irregular grains typified by potato-like grains.

The silver halide emulsion used in the present invention may be prepared by subjecting grains to a rounding treatment as disclosed in European Patent Nos. 96,727Bl and 64,412B1, or by West German Patent 2,306,447C2. JP-A-60-
The surface may be modified as disclosed in 221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532, JP-A-60-22132
0 or U.S. Pat. No. 4,643,966.

The grain size of the emulsion used in the present invention is determined by the equivalent circle diameter of the projected area using an electron microscope, the equivalent sphere diameter of the particle volume calculated from the projected area and the grain thickness, or the equivalent sphere diameter of the volume by the Coulter counter method. Can be evaluated. It can be used by selecting from a wide range from ultrafine particles having a sphere equivalent diameter of 0.01 μm or less to coarse particles exceeding 10 μm. Preferably 0.
That is, grains having a size of 1 to 3 microns are used as photosensitive silver halide grains.

The emulsion used in the present invention may be a polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution, depending on the purpose. As a scale representing the size distribution, a variation coefficient of a circle equivalent diameter of a projected area of a particle or a sphere equivalent diameter of a volume may be used. When a monodispersed emulsion is used, the coefficient of variation is 25% or less,
It is more preferable to use an emulsion having a size distribution of 20% or less, more preferably 15% or less.

In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes are mixed in the same layer in an emulsion layer having substantially the same color sensitivity. Alternatively, it can be applied in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P.Gl.
afkides, Chimie et Physique Photographique, Paul M
ontel, 1967), Duffin, "Photographic Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emulsion C)
Hemistry (Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikuman et al., Focal Press (VLZeli)
kamn et al, Making and Coating Photographic Emulsi
on, Focal Press, 1964). A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled method. The double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, as described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is more preferable. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. It is also effective in some cases to add fine particles having various halogen compositions to modify the surface.

A method for converting most or a very small portion of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,771.
142,900, European Patent 273,429, 27
No. 3,430, West German Patent No. 3,819,241 and the like. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt.

In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1
469,480; U.S. Pat. No. 3,650,757;
The particle formation method of changing the concentration or changing the flow rate as described in JP-A-4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time.

A mixer for reacting a solution of a soluble silver salt with a soluble halide salt is disclosed in US Pat. No. 2,996,287.
Nos. 3,342,605 and 3,415,650
No. 3,785,777, West German published patent 2,55
6,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver salt and the halide salt, or can be added together with the halide salt, the silver salt or the peptizer, and It can also be introduced inside.

Examples of these compounds include ammonia, thiocyanate (rhodancali, rhodanammonium, etc.), and organic thioether compounds (for example, US Pat. No. 3,574,574).
No. 628, No. 3,021,215, No. 3,057,7
No. 24, No. 3,038,805, No. 4,276, 37
Nos. 4, 4,297,439 and 3,704,130
No. 4,782,013, JP-A-57-10492.
Compounds described in No. 6, etc. ) And thione compounds (for example, tetra-substituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. No. 4,221,863, and the like; and thione compounds described in JP-A-53-144319. Compound, a mercapto compound capable of promoting the growth of silver halide grains described in JP-A-57-202531, and an amine compound (for example, JP-A-54-1031).
No. 0717).

It is advantageous to use gelatin as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives A variety of synthetic hydrophilic polymer substances such as homo- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As gelatin, besides lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan,
No. 16, P30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used. JP-A-1-158426
The use of the low-molecular-weight gelatin described in (1) is preferable for preparing tabular grains.

The silver halide emulsion was washed with water for desalting,
It is preferable to use a newly prepared protective colloid dispersion. The temperature of washing can be selected according to the purpose, but 5 ℃ ～ 50 ℃
It is preferable to select within the range. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

It is preferable to add a metal ion salt during the preparation of a silver halide emulsion, for example, during grain formation, in a desalting step, during chemical sensitization, and before coating. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the whole grain and a method of doping only the core part, only the shell part, only the epitaxial part, or only the base grain of the grain can be selected. Mg, Ca, Sr, Ba, A
1, Sc, Y, La, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b, Bi, etc. can be used. These metals can be added as long as they can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, hexacoordinate complex salts, and tetracoordinate complex salts. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO
₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ],
(NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH
₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) _{6 and the} like. Preferably halogen, H
It can be selected from among ₂ O, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds. A method of adding a chalcogen compound during preparation of an emulsion as described in U.S. Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains used in the present invention are at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, and reduction sensitization. Can be applied in any step of the production process of the silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion used in the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose.

Chemical sensitization which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described in TH James, The Photographic Process, 4th Edition, published by Macmillan. , 197
7 years, (THJames, The Theory of the Photographic
Process, 4th ed, Macmillan, 1977), using active gelatin, as described in pages 67-76, or as described in Research Disclosure Item 12008 (1977).
Item 13452 (June 1975); Same
Item 307105 (11/1989), US Patent No. 2,6
42,361, 3,297,446, 3,77
No. 2,031, No. 3,857,711, No. 3,90
Nos. 1,714, 4,266,018, and 3,
No. 904,415 and British Patent 1,315,75.
As described in No. 5, sulfur, selenium, tellurium at pAg 5-10, pH 5-8 and temperature 30-80 ° C.
It can be performed with gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers.

In sulfur sensitization, an unstable sulfur compound is used, and specifically, thiosulfate (eg, hypo),
Thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanines, mercaptos, thioamides, thiohydantoins, 4-oxo-oxazolidin-2-thiones, di- or polysulfides, polythioic acid Salts and elemental sulfur, and U.S. Patent Nos. 3,857,711;
Known sulfur-containing compounds described in 018 and 4,054,457 can be used. Sulfur sensitization is often used in combination with noble metal sensitization.

The preferred amount of sulfur sensitizer used for silver halide grains is 1 × 10 ^-7 to 1 × 10 ^-7 per mol of silver halide.
1 × 10 ⁻³ mol, more preferably 5 × 10 ⁻⁷
１1 × 10 ^-4 mol.

In the selenium sensitization, a known unstable selenium compound is used, for example, US Pat. No. 3,297,44.
No. 6,297,447 and the like, and specific examples thereof include colloidal metal selenium and selenoureas (eg, N, N-dimethylselenourea, tetramethylselenourea). Etc.), seleno ketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), Selenium compounds such as selenophosphates (for example, tri-p-tolyl selenophosphate) can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

The amount of the selenium sensitizer to be used varies depending on the type of selenium compound used, the type of silver halide grains, the conditions of chemical ripening and the like, but is generally from 10 ^-8 to 1 per mol of silver halide.
^0-4 mol, preferably about ^10-7 to ^10-5 mol is used.

The tellurium sensitizers used in the present invention include Canadian Patent No. 800,958 and British Patent Nos. 1,2.
Nos. 95,462 and 1,396,696, Japanese Patent Application No. 2-
Compounds described in, for example, 333819 and 3-131598 can be used.

In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
Known compounds such as gold selenide can be used.
The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂
PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

The emulsion used in the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol per mol of silver halide;
More preferably, it is 5 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol. The preferred range of the palladium compound is 5 × 10 ^-7 to 1
× 10 ^-3 mol. A preferable range of the thiocyan compound or the selenocyan compound is 1 × 10 ^{−6 to} 5 × 10 ^−2.
Is a mole.

It is preferable to carry out reduction sensitization of the silver halide emulsion during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method in which a reduction sensitizer is added to a silver halide emulsion, or a pAg 1 called silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8 to 11, which is called high pH ripening, can be selected. Also, two or more methods can be used in combination.

As the reduction sensitizer, known reduction sensitizers such as stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidine sulfinic acid, silane compounds and borane compounds are selected. And two or more compounds can be used in combination. Stannous chloride as reduction sensitizer,
Aminoiminomethanesulfinic acid (common name: thiourea dioxide), dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known as azaindene, azapyridazine, and aspapirimidine, which are known to suppress fog and increase sensitivity in the course of chemical sensitization. Examples of chemical sensitization aids are described in U.S. Pat. Nos. 2,131,038 and 3,411,
Nos. 914 and 3,554,757, JP-A-58-12
No. 6526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, 1
38-143.

It is preferable to use an oxidizing agent for silver during the emulsion production process. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ions generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide or silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H
_{2 O 2, Na 4 P 2} O 7 · 2H 2 O 2, 2Na 2 SO 4 · H 2 O 2
2H ₂ O), peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂
C ₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compound (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] .3H ₂ O, 4K ₂ SO ₄
・ Ti (O ₂ ) OH ・ SO ₄・ 2H ₂ O, Na ₃ [VO (O ₂ )
_{(C 2 H 4) 2 ·} 6H 2 O), permanganate (eg, K
Oxyacids such as MnO ₄ ), chromates (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and salts of high-valent metals (Eg, potassium hexacyanoferrate) and thiosulfonate.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T). , Chloramine B). It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (1-phenyl-5-mercaptotetrazole, 1-
(5-methylureidophenyl) -5-mercaptotetrazole and the like); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes and tetraazaindenes (particularly, Many compounds known as antifoggants or stabilizers, such as 4-hydroxy-6-methyl (1,3,3a, 7) tetraazaindene), pentaazaindenes and the like can be added. For example, US Pat. No. 3,954,474
No. 3,982,947, JP-B-52-28660
Those described in the item can be used. One of the preferred compounds is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose.

The photographic emulsion used in the present invention is spectrally sensitized by a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzene An imidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862 and 4,026,707, British Patent Nos. 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-5
Nos. 2-110618 and 52-109925.

In addition to the sensitizing dye, the emulsion may contain a dye having no spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, this is done after completion of chemical sensitization but before coating, but US Pat. No. 3,628,969.
As described in JP-A-58-113,928, spectral sensitization can be carried out simultaneously with chemical sensitization by adding a chemical sensitizer at the same time as described in JP-A-58-113,928. Can be carried out prior to chemical sensitization as described in (1), or can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, these compounds can be added separately, i.e., some of these compounds can be added prior to chemical sensitization and the remainder can be chemically modified. It is also possible to add after sensitization, see US Pat.
At any time during the formation of silver halide grains, including the method disclosed in US Pat. The addition amount is from 4 × 10 ⁻⁶ to 8 × 10 ⁻³ per mol of silver halide.
The silver halide grains can be used in an amount of about 5 × 10 ^{−5 in} the case of a more preferable silver halide grain size of 0.2 to 1.2 μm.
~ 2 × 10 ^-3 moles is more effective.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978),
Item 18716 (November 1979) and Item 30710
5 (January, 1989), and the relevant locations are summarized in the table below.

[0178]

[Table 1]

The total coated silver amount of the light-sensitive material of the present invention is preferably 0.003 to 12 g per m ^{2 in} terms of silver. In the case of a transmission material such as a color negative film, the weight is preferably 1 to 12 g, more preferably 3 to 10 g. For reflective materials such as color paper, 0.003 ~
1 g is preferable in terms of rapid processing and low replenishment. In this case, the amount of each layer added is 0.001 to 0.4 per photosensitive layer.
g is preferred.

In the present invention, when the amount of silver applied to each photosensitive layer is less than 0.001 g per 1 m ² , the dissolution of the silver salt proceeds and a sufficient color density cannot be obtained.

The total amount of gelatin in the light-sensitive material of the present invention is 1 m
1.0 to 30 g per ² and preferably 2.0 to ² g
0 g. In the swelling of the present light-sensitive material using an alkaline solution having a pH of 12, the saturated swelling film thickness (the maximum swelling film thickness of 9)
(0%) is preferably 15 seconds or less, and more preferably 10 seconds or less. The swelling ratio [(maximum swollen film thickness−film thickness) / film thickness × 100] is 50 to
300% is preferable, and especially 100-200% is preferable.

As the antibacterial and antifungal agents usable in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer.

The cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy.

As the cathode ray tube used for the image exposure, various luminous bodies which emit light in a spectral region are used as necessary. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used.
The spectral region is not limited to the above red, green, and blue, and a light emitter that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a luminous body which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signals of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a filter for cutting a color other than that color (plane sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for high image quality.

The photosensitive material of the present invention is a second harmonic generation light source (SHG) in which a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source is combined with a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. In particular, it is preferable to use a semiconductor laser in order to design a device that is compact, inexpensive, has a long life, and has high stability.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red.

The exposure time in such scanning exposure is as follows:
If the pixel size is defined as the exposure time when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, and more preferably 10 ^-6 seconds or less. In particular, the exposure time per pixel is 10 ^-8 to 10 ^-4 seconds,
Exposure by scanning exposure in which adjacent rasters overlap with each other is preferable in that reciprocity failure is improved.

The preferred scanning exposure method applicable to the present invention is described in detail in JP-A-7-104448, column 76, line 6 to column 77, line 41.

Examples of the image forming method using a photosensitive material containing a color developing agent precursor of the present invention include an activator processing method in which, after exposure, development is performed with an alkaline processing solution containing no color developing agent, an auxiliary developing agent / There are a method of processing with a processing solution containing a base, a method of developing the alkaline processing solution on a photosensitive material by a diffusion transfer method, and a method of processing by thermal development. When performing the activator processing, the photosensitive material is activator development (color development), desilvering, and washing with water,
Or it is stabilized.

Activator processing refers to a processing method in which a color developing agent precursor is incorporated in a light-sensitive material and is developed with a processing solution containing no color developing agent precursor.
In the present invention, the "activator liquid" is characterized in that it does not substantially contain a color developing agent, and may contain other components (alkali, halogen, chelating agent, etc.). In some cases, it is preferable that a reducing agent is not contained in order to maintain processing stability. In this case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites, and the like are not substantially contained.

Here, "substantially not contained" means preferably 0.5 mmo1 / liter or less, more preferably 0.1 mmo1 / liter or less. In particular, it is preferable not to contain at all. PH of alkaline processing liquid
Is preferably from 9 to 14, and particularly preferably from 10 to 14.
Thirteen.

The activator processing light-sensitive material and its processing can be performed by using the color developing agent precursor of the present invention instead of or together with the built-in hydrazine compound, for example, as described in JP-A-8-234388. 7-33
Nos. 4190, 7-334192, 7-334419
Nos. 7 and 7-344396 are applied.

The activator liquid may contain halogen ions such as chlorine ions, bromine ions and iodine ions, but preferably does not contain them. Here, the halide may be directly added to the activator solution, or may be eluted from the photosensitive material into the activator solution during the development processing using the activator solution. The activator liquid used in the present invention preferably has a pH of 8 to 13, more preferably 9 to 12.

To maintain the above pH, it is preferable to use various buffers. Carbonate, phosphate, tetraborate,
It is preferred to use hydroxybenzoates. The amount of the buffer added to the activator solution is preferably at least 0.05 mol / l, particularly preferably from 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the activator liquid as an agent for preventing precipitation of calcium or magnesium, or for improving the stability of the activator liquid. The addition amount of these chelating agents may be an amount sufficient to mask metal ions in the activator solution, for example, 0.1 g to 10 g per liter.
g.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds are used. The addition amount of the nitrogen-containing heterocyclic compound is 1 × 10 ⁻⁵
Mol / l to 1 × 10 ⁻² mol / l, preferably 2.5 × 10 ⁻⁵ mol / l to 1 × 10 ⁻³ mol / l
Liters.

An optional development accelerator can be added to the activator if necessary. The activator liquid preferably contains a fluorescent whitening agent. In particular, it is preferable to use a 4,4'-diamino-2,2'-disulfostilbene compound.

The processing temperature of the activator solution applied to the present invention is 20 ° C. to 50 ° C., preferably 30 ° C. to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. It is preferable that the replenishment amount is small,
^{2 to} 15 ml to 600 ml, preferably 25 ml to
The volume is 200 ml, more preferably 35 ml to 100 ml.

After the development, a desilvering treatment is performed. The desilvering process includes a fixing process and a bleaching and fixing process. When performing the bleaching and fixing processes, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Also, without desilvering after development,
In some cases, it is also preferable to carry out a stabilization treatment to stabilize a silver salt or a color image.

Examples of the bleaching agent used in the bleaching solution or the bleach-fixing solution include iron (III), cobalt (III), chromium (I
V), compounds of polyvalent metals such as copper (II), peracids, quinones and nitro compounds. Among these, iron aminopolycarboxylates such as iron (III) complex salt of ethylenediaminetetraacetate; iron (III) complex salt of 1,3-diaminopropanetetraacetate
(III), hydrogen peroxide, persulfate and the like are preferable from the viewpoint of rapid treatment and prevention of environmental pollution.

The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is from 3 to 8, preferably from 5 to 7. The pH of the bleaching solution using persulfate or hydrogen peroxide is used at 4 to 11, preferably 5 to 10. A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary. In the bleaching solution, the bleach-fixing solution and the fixing solution, conventionally known additives such as a rehalogenating agent, a pH buffering agent and a metal corrosion inhibitor can be used. In particular, it is preferable to contain an organic acid having an acid dissociation constant (pKa) of 2 to 7 in order to prevent bleaching stain. Examples of a fixing agent used in a fixing solution or a bleach-fixing solution include thiosulfates, thiocyanates, thioureas, a large amount of iodide salts and JP-A-4-36.
No. 5037 No. 11 to 21 and No. 5-66540 No. 108
Examples include nitrogen-containing heterocyclic compounds having a sulfide group, mesoionic compounds, and thioether compounds described on pages 8 to 1092.

As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. The fixing solution or the bleach-fixing solution may further contain various fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like.

The processing temperature in the desilvering step is from 20 ° C. to 50 ° C., preferably from 30 ° C. to 45 ° C. Processing time is 5 seconds to 2
Minutes, preferably 10 seconds to 1 minute. Replenishment rate is desirably small, but the photosensitive material 1 m ² per 15~600m
1, preferably 25 to 200 ml, more preferably 35 to 100 ml. It is also preferable to perform the treatment without replenishment, to the extent that the evaporation amount is supplemented with water.

The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process, JP-A-57-8543 and JP-A-58-1483 are used.
Nos. 4 and 60-220345, and JP-A-5-220345.
8-127926, 58-13837, 58
All known methods described in JP-A-140741 can be used. Further, a washing step and a stabilizing step in which a stabilizing bath containing a dye stabilizing agent and a surfactant represented by processing of a color light-sensitive material for photographing is used as a final bath may be performed.

The washing solution and the stabilizing solution include sulfites; hard water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid; metal salts such as Mg salt, Al salt and Bi salt; Agents; hardeners; pH buffering agents; fluorescent whitening agents; silver salt-forming agents such as nitrogen-containing heterocyclic compounds;

Examples of the dye stabilizer of the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.

The pH of the washing or stabilizing solution is from 4 to 9, preferably from 5 to 8. The processing temperature is generally from 15 to 45 ° C, preferably from 25 to 40 ° C. The processing time is generally from 5 seconds to 2 minutes, preferably from 10 seconds to 40 minutes.
Seconds.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step. The amount of the washing water and / or the stabilizing solution can be set in a wide range depending on various conditions, but the replenishing amount is preferably 15 ml to 360 ml per 1 m ² of the light-sensitive material.
ml to 120 ml are more preferred. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks and carry out the method in a multistage countercurrent system.

In the present invention, water obtained by treating an overflow liquid or a liquid in a tank with a reverse osmosis membrane to save water can be used. For example, the treatment by reverse osmosis is preferably performed on water in the second and subsequent tanks for multi-stage countercurrent washing and / or stabilization.

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening the stirring are described in JP-A-62-183460 and JP-A-62-1834.
No. 61, a method of impinging a jet jet of a processing liquid on an emulsion surface of a light-sensitive material, a method of increasing a stirring effect by using a rotating means disclosed in JP-A-62-183461, and a wiper blade provided in a liquid A method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means includes an activator solution, a bleaching solution, a fixing solution, a bleach-fixing solution,
It is useful for both the stabilizing solution and washing with water. These methods are effective in that the supply of the effective component in the liquid into the photosensitive material and the diffusion of the unnecessary component of the photosensitive material are promoted.

In the present invention, the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] of any bath shows excellent performance in any state, but from the viewpoint of the stability of the liquid components. The liquid aperture ratio is preferably from ⁰ to 0.1 cm ^-1 . In a continuous process, 0.001 cm ^{-1 to} 0.0
The range is preferably 5 cm ^-1 , more preferably 0.002.
The automatic developing machine used for the light-sensitive material of the present invention having a cm.sup.- ^{1 to} 0.03 cm.sup.- ¹ is a light-sensitive material conveying means described in JP ^{-A -} 60-191257, JP ^{-A -} 60-191258, and JP ^{-A -} 60-191259. It is preferable to have Such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for shortening the processing time of each step and reducing the replenishing amount of the processing solution. In order to shorten the processing time, it is preferable to shorten the crossover time (air time). For example, FIGS. 4, 5 or 6 of JP-A-4-86659 and FIG. 4 of JP-A-5-66540. Alternatively, a method of conveying each processing time shown in FIG. 5 through a blade having a shielding effect is preferable.

When the respective processing solutions are concentrated by evaporation in the continuous processing, it is preferable to add water to correct the concentration.

The processing time of the step in the present invention means the time required from the start of processing of the photosensitive material in one step to the start of processing in the next step. The actual processing time in an automatic developing machine is usually determined by the linear speed and the capacity of the processing bath.
/ Min to 4000 mm / min. In particular, in the case of a small developing machine, it is preferably from 500 mm / min to 2500 mm / min.

The total processing step, that is, the processing time from the developing step to the drying step is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the activator solution to when it comes out of the drying unit of the processor.

Various additives are used in the treatment applied to the present invention, and are described in more detail in Research Disclosure Item 36544 (September, 1994). Was.

Processing Agent Type Page Antifoggant 537 Chelating Agent 537 Right Column Buffer 537 Right Column Surfactant 538 Left Column and 539 Left Column Bleaching Agent 538 Bleaching Accelerator 538 Right Column to 539 Left Column Bleaching Chelating Agent 539 Left Column Rehalogenating agent 539 Left column Fixing agent 539 Right column Fixing agent preservative 539 Right column Fixing chelating agent 540 Left column Stabilizing surfactant 540 Left Stabilizing scum inhibitor 540 Right Stabilizing chelating agent 540 Right Antibacterial and deodorant 540 Right Color image stabilizer 540 Right Activator solution development processing in a diffusion transfer system is known in the art as an instant processing system and includes at least one photosensitive layer / dye-forming layer. (Preferably, the photosensitive layer and the dye-forming layer are composed of the same layer) and the photosensitive element / dye-forming layer. A diffusible dye an activator solution of the following thickness 500μm in the light-sensitive material having a image-receiving element in the support or another support on having a capture-mordant mordanted layer, preferably 50μm
This refers to developing processing with a liquid thickness of 200 μm.

When an auxiliary developing agent is incorporated, it is preferable that the activator solution for producing or storing the processing solution does not contain the auxiliary developing agent. In the case of the diffusion transfer system, the pH of the activator solution is preferably 10 to 14
And particularly preferably 12 to 14. For the process of instant photographic materials, see The Theory.
of Photographic Process
The fourth edition (1977, Makmi11an) and the specific structure of the film unit are disclosed in
No. 226649.

The dye image-receiving layer and the mordant contained therein are described in JP-A-61-252551, US Pat. Nos. 2,548,564, 3,756,814 and 4,124,386. No. 3,625,694. As for the neutralizing layer for lowering the pH of the photosensitive material after the activator solution is developed,
-122753, U.S. Pat. No. 4,139,383,
RD-No. 16102, the timing layer used in combination with the neutralizing layer is disclosed in
No. 4-136328, U.S. Pat. No. 4,267,262.
No. 4,009,030 and 4,268,60
No. 4. As the emulsion, any emulsion can be used. Preferred autopositive emulsions for photographic light-sensitive materials are described in JP-A-7-333770 and JP-A-7-333.
No. 771 and the like. In addition, if necessary, a light shielding layer, a reflection layer, an intermediate layer, an isolation layer, an ultraviolet absorbing layer,
A filter layer, an overcoat layer, an adhesion improving layer, and the like can be provided.

The processing solution for processing the above photosensitive material is as follows:
It contains processing components necessary for development, and usually contains a thickener to develop uniformly on a light-sensitive material. Thickening agents such as carboxymethylcellulose and hydroxyethylcellulose are preferable as the thickener. Details of the photosensitive layer and the processing solution are described in JP-A-7-33.
No. 3771.

The heat treatment in the heat development of the light-sensitive material is known in the art and can be applied to the light-sensitive material of the present invention. The photothermographic material and its process are described, for example, in Photo Industry Fundamentals (1979, published by Corona Co., Ltd.).
53-555 pages, video information published in April 1978, 40
Page, Nobletts Handbook of Ph
Otography and Reprography
7th Ed. (VanNostr and Rei
nhod Company), pages 32-33, U.S. Patent Nos. 3,152,904 and 3,301,678.
No. 3,392,020 and 3,457,075
Nos. 1,131,108 and 1,16
7,777, and Research Disclosure, June 1978, pages 9-15 (RD-17029).
It is described in.

The light-sensitive material of the present invention may contain, for the purpose of accelerating silver development and a dye-forming reaction, US Pat. No. 4,514,493.
No. 4,657,848 and Known Technology No. 5 (March 22, 1991, Aztec Co., Ltd.), pp. 55-86, and European Patent Publication 210,660. U.S. Pat. No. 4,740,
It is preferable to apply the base generation method described in No. 445.

To the light-sensitive material of the present invention, a thermal solvent described in US Pat. Nos. 3,347,675 and 3,667,959 may be added for the purpose of accelerating thermal development. .

When the light-sensitive material of the present invention is subjected to heat treatment, in order to promote development and / or diffusion transfer of the processing material,
Water, an aqueous solution containing an inorganic alkali metal salt or an organic base,
It is also preferable to include a low-boiling solvent or a mixed solvent of a low-boiling solvent and water or the above-mentioned basic aqueous solution in a light-sensitive material or a processing sheet and heat-treat it. Examples of the method using water include JP-A-63-144354 and JP-A-63-144.
No. 35, 62-38460, JP-A-3-21055
No. 5, JP-A-62-253159 and 63-8554.
No. 4, EP 210,660 and US Pat. No. 4,740,445.

The present invention relates to JP-A-7-261336, JP-A-7-268045, JP-A-8-30103, and JP-A-8-46.
The invention can also be applied to the photothermographic materials and photothermographic image forming methods described in JP-A-822-822 and JP-A-8-97344.
The heating temperature in the thermal development step is about 50 ° C to 200 ° C,
Particularly, a temperature of 60 ° C to 150 ° C is useful. The water saving technique applied to the present invention is described in detail in Research Disclosure Item 36544 (September 1994) 54
It is described in the right column of page 0 to the left column of page 541.

[0227]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it should be understood that the present invention is not limited to these Examples.

(Example 1) Alkaline solution (THF / Briton-Robinson buffer = 3/2, pH = 1)
Stability at 0, 30 ° C was observed.

The following model compounds 1, 2 and 3 were used, and their decomposition and the resulting 4-octylaniline (hereinafter simply referred to as aniline) were observed and quantified by HPLC. As a comparative compound, compound A having a skeletal structure described in US Pat. No. 5,538,834 was used. FIG. 1 shows the measurement results.

[0230]

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In FIG. 1, the dashed line A represents the remaining amount of the comparative compound A, the dashed line B represents the amount of aniline released (composed amount) from the comparative compound A, the solid line C represents the remaining amount of the compound 1 of the present invention, and the solid line D represents the present invention. 2 shows the amount of aniline released from Compound 1.

As is clear from FIG. 1, the comparative compound decomposed gradually in the alkaline solution, whereas the compound of the present invention was stably present in the alkaline solution and did not release aniline.

(Example 2) Alkaline 0.3% hydrogen peroxide solution (THF / Britton-Robinson buffer =
3/2, pH = 10, 25 ° C.) was monitored over time by HPLC using a model compound. The measurement results are shown in FIGS. In FIG. 2, solid line A indicates the remaining amount of compound 1 of the present invention, solid line B indicates the remaining amount of compound 2 of the present invention, and solid line C indicates the remaining amount of compound 3 of the present invention. In FIG. 3, the solid line A indicates the amount of aniline released from the compound 1 of the present invention (produced amount), the solid line B indicates the amount of released aniline from the compound 2 of the present invention (produced amount), and the solid line C indicates the compound 3 of the present invention. The amount of aniline released from (production amount). Figures 2 and 3
As can be seen, the compounds of the present invention release aniline in alkaline hydrogen peroxide solution.

From these results, it can be seen that the compound of the present invention is a compound which can react only in the presence of a peracid and a peroxide and can release a desired photographically useful group. It is clear that the compounds of the present invention are stable in the absence of peracids and peroxides, and can achieve both activity during processing and stability during storage.

Example 3 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and two types of photographic constituent layers were further applied. Thus, a photographic paper (100) having the following two-layer structure was produced. The coating solution was prepared as follows. The following average grain size is defined as the average value of the diameter of the same circle as the projected area of the grain.

Coating solution for first layer 4.88 g of coupler (ExY1), solvent (So1v-
1) Dissolve 5.0 Og in ethyl acetate and add this solution to 10
An emulsified dispersion A was prepared by emulsifying and dispersing in 40 g of a 16% gelatin solution containing 5% sodium dodecylbenzenesulfonate and citric acid.

On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of silver emulsion A having a large size having an average grain size of 0.88 μm and emulsion A having a small size of 0.70 μm (silver molar ratio), grain size distribution) Are 0.08 and 0.1, respectively.
0, 0.3 mol% of silver bromide in each size emulsion was localized and contained on a part of the surface of the grain having silver chloride as a base material). This emulsion contains the following blue-sensitive sensitizing dyes A,
B and C were added to the large-size emulsion A in an amount of 1.4 × 10 ^-4 mole and to the small-size emulsion A in an amount of 1.7 × 10 ^-4 mole per mole of silver. . The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer so as to have the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

The coating solution for the second layer was prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

In each layer, Cpd-2, Cpd-3, Cpd
pd-4 and Cpd-5 each having a total amount of 15.0 mg /
m ² , 60.0 mg / m ² , 50.0 mg / m ² and 1
It was added to a concentration of 0.0 mg / m ² .

The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of the first layer.

[0241]

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Further, 1 × (5-methylureidophenyl) -5-mercaptotetrazole was added in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide.

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support A Polyethylene laminated paper [The polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultra blue)] First layer Silver chlorobromide emulsion A 0.20 Gelatin 50 Yellow coupler (ExY1) 0.61 Solvent (Solv-1) 0.63 Second layer (protective layer) Gelatin 1.01 Acrylic-modified copolymer of polyvinyl alcohol (Modification degree: 17%) 0.04 Liquid paraffin 02 Surfactant (Cpd-1) 0.01 The yellow coupler in the first layer coating solution was replaced with the yellow coupler shown in Table 2 in an equimolar amount, and the precursor of the developing agent shown in Table 2 was used for the coupler. The sample (10) was prepared in exactly the same manner as the preparation of the sample (100) except that
1) to (108) were prepared.

Further, silver chlorobromide emulsion A in the coating solution of the first layer was used.
Is replaced with the silver chlorobromide emulsion B shown below by an equivalent silver amount, the yellow coupler is replaced by an equivalent mole with the magenta coupler shown in Table 2, and the precursor of the developing agent shown in Table 2 is replaced with the coupler. Samples (200) to (204) were prepared in exactly the same manner as in the preparation of sample (100) except that they were added in moles.

Silver chlorobromide emulsion B: cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.55 μm and small-size emulsion B having an average grain size of 0.39 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and the emulsions of each size contained 0.8 mol% of AgBr locally on a part of the grain surface containing silver chloride as a substrate. The following spectral sensitizing dyes were used for silver chlorobromide emulsion B, respectively.

[0247]

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(Sensitizing dye D was used in an amount of 3.0 × 10 ^-4 mol for a large-sized emulsion, 3.6 × 10 ^-4 mol for a small-sized emulsion, and Sensitizing dye E was used in an amount of 4.0 × 10 ^-5 mol per mol of silver halide and 7.0 mol per mol of silver halide.
× 10 ^-5 mol, and 2.0 × 10 ^-4 mol of sensitizing dye F per mol of silver halide per mol of silver halide and 2.8 × 10 ^-4 mol per mol of silver emulsion. Further, silver chlorobromide emulsion A in the coating solution for the first layer was replaced with silver chlorobromide emulsion C shown below with an equivalent silver amount, and the yellow coupler was equimolar to the cyan coupler shown in Table 2. Samples (300) to (304) were prepared in exactly the same manner as Sample (100) except that the precursor of the developing agent shown in Table 2 was added in an equimolar amount to the coupler.

Silver chlorobromide emulsion C: a 1: 4 mixture (Ag molar ratio) of a cubic, large size emulsion C having an average grain size of 0.5 μm and a small size emulsion of 0.41 μm. The variation coefficients of the grain size distribution were 0.09 and 0.11, and each of the emulsions contained 0.8 mol% of AgBr locally on a part of the grain surface containing silver chloride as a substrate. The following spectral sensitizing dyes were used for silver chlorobromide emulsion C, respectively.

[0250]

Embedded image

(Per mol of silver halide, 5.0 × 10 ^-5 mol was added to the large-size emulsion, and 8.0 × 10 ^-5 mol was added to the small-size emulsion.)

[0252]

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[0253]

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[0254]

Embedded image

[0255]

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Two samples prepared as described above were prepared, one of them was subjected to forced thermostat at a temperature of 50 ° C. and a humidity of 70% for one week, and the other was simultaneously frozen and stored. After the sample after the thermotest and the sample stored in a frozen state are processed in the following processing step 1, for the samples (100) to (108), the yellow density difference ΔD ^B between the sample subjected to the thermotest and the sample stored in a frozen state min, samples (200) to (20)
For 4), magenta density difference ΔD ^G min, and for samples (300) to (304), cyan density difference ΔD
^R min was measured respectively. Table 2 shows the results. The smaller this value is, the smaller the stain due to the storage over time is.

Processing Step 1 Processing Step Temperature Time Bleach-fix 40 ° C. 45 seconds Rinse Room temperature 90 seconds Bleach-fix solution Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g 1000 ml pH with addition of water (25.C / acetic acid and aqueous ammonia) 5.8 Rinse solution 0.02 g of chlorinated sodium isocyanurate 0.02 g deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5 Untreated samples were sampled using a FWH type photometer manufactured by Fuji Film Co., Ltd. (color temperature of light source: 3200 ° K).
For (108), a blue filter for sensitometry, and for samples (200) to (204), for a green filter for sensitometry, samples (300) to
For (304), gradation exposure was given by a red filter for sensitometry.

The exposed sample was processed in the following processing step 2 using the following processing liquid.

Processing Step 2 Processing Step Temperature Time Development 40 ° C. 45 seconds Bleaching and Fixing 40 ° C. 45 seconds Rinse Room temperature 90 seconds Developing solution (alkali activating solution containing hydrogen peroxide) Water Potassium carbonate 600 ml Hydrogen peroxide (30%) 20 ml Chloride Potassium 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml pH (at 25 ° C./sulfuric acid) 10.5 The bleach-fixing solution and the rinsing solution described above were used.

The maximum color density portion and the minimum color density portion of the processed sample were blue light for samples (100) to (108), green light for samples (200) to (204), and sample (100) to (204). 300) to (304) were measured with red light. Table 2 shows the difference (ΔDmax) between the maximum color density and the minimum color density.

[0261]

[Table 2]

As is clear from Table 2, no color development occurs when the treatment is carried out with a processing solution containing no color developing agent. When the comparative compound 1 or 2 is used, a color develops, but a stain (ΔDmin) due to the formation of a dye occurs during storage. Further, even under such storage conditions, the precursor of the color developing agent of the present invention hardly generates stain due to dye formation,
Moreover, the density difference between the maximum color density and the minimum color density is large,
It can be seen that an image excellent in discrimination can be obtained.

Example 4 Samples (100) to (3) of Example 3
(104), Samples (200) to (202), Sample (30)
0) to (302) with respect to hydrogen peroxide (30
%) 20 ml of magnesium monoperoxyphthalate 2
The ΔDmax was evaluated in the same manner as in Example 3 except that g was replaced with g. Table 3 shows the results.

[0264]

[Table 3]

When a developing solution to which magnesium monoperoxyphthalate is added instead of hydrogen peroxide is used,
It was found that the sample using the precursor of the color developing agent of the present invention provided an image excellent in discrimination, and exhibited better color development than the case using hydrogen peroxide.

[0266]

The novel aromatic boron derivative compound of the present invention reacts only in the presence of a peroxide to release an intended photographic useful group, and in the absence of a peroxide, It is a useful compound that is stable and can achieve both activity during treatment and stability during storage. Further, the silver halide photographic light-sensitive material and the image forming method of the present invention have almost no stain due to dye formation even under the condition of forced thermostat at a temperature of 50 ° C. and a humidity of 70% for one week, and have a maximum color density. The density difference between the minimum color densities is large, and an image excellent in discrimination can be obtained.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram for explaining a result obtained by measuring stability in an alkaline solution by HPLC using a model compound.

FIG. 2 is a graph for explaining the result of measuring the reactivity in an alkaline 0.3% hydrogen peroxide solution by HPLC using a model compound, and the reaction rate (%) of the compound is shown. It is shown by the residual rate (%).

FIG. 3 is a diagram for explaining the result of measuring the reactivity in an alkaline 0.3% hydrogen peroxide solution by HPLC using a model compound, and shows the formation of aniline released from the compound. It shows the rate (%).

[Explanation of symbols]

In FIG. 1, line A is the residual amount of comparative compound A, line B is the amount of aniline released from comparative compound A (produced amount), line C is the residual amount of compound 1 of the present invention (produced amount), and line D is It represents the release amount (production amount) of aniline from compound 1 of the invention. FIG.
, The A line represents the remaining amount of the compound 1 of the present invention, the B line represents the remaining amount of the compound 2 of the present invention, and the C line represents the remaining amount of the compound 3 of the present invention. In FIG. 3, line A is the release amount (production amount) of aniline from compound 1 of the present invention, and line B is compound 2 of the present invention.
And the C line represents the amount of aniline released from Compound 3 of the present invention (generated amount).

Claims (6)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, characterized by containing a compound represented by the following general formula (1). Photosensitive material. General formula (1) (R) ₂ B-Ar-CH _2- (L) _n -PUG In general formula (1), Rs are each independently a hydroxyl group,
Represents an alkoxy group, an aryloxy group and an aryl group. Two Rs may combine with each other to form a ring. A
r represents a substituted or unsubstituted aryl group or heterocyclic group, and L represents a linking group. PUG represents a photographic useful group, and n represents an integer of 0 to 3. When R is a hydroxyl group,
The compound of the general formula (1) may have a triboroxane structure by a dehydration reaction between three molecules. 2. The silver halide photographic material according to claim 1, wherein the compound represented by the general formula (1) represented by the general formula (1) is represented by the following general formula (2). Embedded image In the general formula (2), R ¹ independently represents a hydroxyl group, an alkoxy group, an aryloxy group, and an aryl group. Two R ¹ may combine with each other to form a ring. R ² represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonylamino group or a substituted amino group, and a hydroxyl group. A plurality of R ² may combine with each other to form a ring. CH ₂ represents a methylene group located at the ortho or para position of the boron atom, and L represents a linking group. PUG represents a photographic useful group, and m represents an integer of 1 to 4. When m is 2 or more, a plurality of R ² may be the same or different. p represents an integer of 0 to 2. When R ¹ is a hydroxyl group, the compound of the general formula (2) may have a triboroxane structure by a dehydration reaction between three molecules. 3. The silver halide photographic material according to claim 1, wherein the compound represented by the general formula (1) represented by the general formula (1) is represented by the following general formula (3). Embedded image In the general formula (3), R ³ is each independently a hydroxyl group,
R ⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acylamino group, a sulfonylamino group, or a hydroxyl group. A plurality of R ³ may combine with each other to form a ring. CH ₂ represents a methylene group located at the ortho or para position of the boron atom. PUG represents a photographic useful group, and r represents an integer of 1 to 4.
When r is 2 or more, a plurality of R ⁴ may be the same or different. When R ³ is a hydroxyl group, the compound of the general formula (3) may have a triboroxane structure by a dehydration reaction between three molecules. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (1) represented by the general formula (1) is represented by the following general formula (4). Embedded image In the general formula (4), R ⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an acylamino group, a sulfonylamino group, or a hydroxyl group. A plurality of R ⁵ may combine with each other to form a ring. CH ₂ represents a methylene group located at the ortho or para position of the boron atom. PUG represents a photographic useful group, and q represents an integer of 1 to 4. When q is 2 or more, a plurality of R ⁵ may be the same or different. The compound of the general formula (4) may have a triboroxane structure by a dehydration reaction between three molecules. 5. The silver halide according to claim 1, wherein PUG in the compounds of formulas (1) to (4) is a color developing agent. Photosensitive material. 6. An image forming method, wherein the silver halide photographic light-sensitive material according to claim 1 is processed in the presence of a peracid or a peroxide.